Composite Material, Gas Adsorbent, and Method for Producing Composite Material

ABSTRACT

A method for producing a composite material containing a porous body having pores inside the porous body and a porous coordination polymer compound, in which the porous body has a network structure of Si—O bonds obtained by copolymerizing a dialkoxysilane and a trialkoxysilane, and the porous coordination polymer compound is carried in the pores of the porous body via a solvent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 16/333,621 filed Mar. 15 2019, which is the UnitedStates national phase of International Application No. PCT/JP2017/035539filed Sep. 29, 2017, that claims priority to Japanese Patent ApplicationNo. 2016-193391 filed Sep. 30, 2016, the disclosure of each of which ishereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION Technical Field

The present invention relates to a composite material, a gas adsorbent,and a method for producing a composite material, and in particular,relates to a composite material on which a porous coordination polymercompound is carried, a gas adsorbent, and a method for producing acomposite material.

Background Art

A porous coordination polymer compound (PCP) is a porous material havingnanopores, in which metal ions and organic ligands form athree-dimensional coordination network, and has various characteristicssuch as a regular pore structure, a high specific surface area, and aflexible structure. For this reason, the PCP is expected to play a roleas a highly designed functional material, and for example, applicationsof the PCP to a gas adsorbent, a gas storage material, and the like havebeen developed.

In practical application of the PCP, a technique for shaping a PCP isessential. Conventionally, several methods are known as a shapingtechnique for a PCP. For example, in Non Patent Literature 1, acomposite obtained by synthesizing a PCP in macropores of a silicamonolith having the macropores has been disclosed. In the PCP of thisliterature, “Cu-BTC” (that is, [Cu₃(BTC)₂] (in this regard, BTC is1,3,5-benzenetricarboxylic acid)) is used, and there is a descriptionthat the composite is a Cu-BTC-SiO₂ monolith.

Further, in Non Patent Literature 2, a composite obtained by mixing aPCP (Cu-BTC) adjusted in advance with a precursor solution of a silicaaerogel and turning the mixture into a gel has been disclosed. In thePCP of this literature, “Cu-BTC” is used similarly as in Non PatentLiterature 1, and there is a description that the silica aerogel issynthesized from tetraethyl orthosilicate (TEOS).

Furthermore, in Non Patent Literature 3, a composite obtained byhardening and molding a paste of bentonite clay and a PCP has beendisclosed. In the PCP of this literature, “MIL-101 (Cr)” (that is,[Cr₃O(OH)(—H₂O)₂(BDC)₃].xH₂O (in this regard, BDC is1,4-benzenedicarboxylic acid)) is used.

In addition, in Non Patent Literature 4, a composite material in which anickel metal skeleton is coated with a PCP by spraying a PCP suspensioncontaining 3 wt % polytetrafluoroethylene (PTFE) as a binder to a foambody of a nickel metal has been disclosed. In the PCP of thisliterature, “MIL-101(Cr)” is used similarly as in Non Patent Literature3.

On the other hand, conventionally, a flexible material called amarshmallow-like gel, which is a copolymer of a bi- or more-functionalalkoxysilane, is known. For example, in Patent Literature 1, a copolymerof an alkoxysilane having a specific partial structure has beendisclosed, and there is a description in Examples that a chelate silicaxerogel is used as a metal-ion removing material.

CITATION LIST Patent Literature

Patent Literature 1: JP 2016-37594 A (claim 1, Example 2, and the like)

Non Patent Literature

Non Patent Literature 1: Song et al., “Porous Cu-BTC silica monoliths asefficient heterogeneous catalysts for the selective oxidation ofalkylbenzenes”, RSC adv., 2014, 4, 30221-30224.

Non Patent Literature 2: Ulker et al., “Novel nanostructured compositesof silica aerogels with a metal organic framework”, Micropor. Mesopor.Mater., 2013, 170, 352-358.

Non Patent Literature 3: Hong et al., “Manufacturing of metal-organicframework monoliths and their application in CO2 adsorption”, Micropor.Mesopor. Mater., 2015, 214, 149-155.

Non Patent Literature 4: Ren et al., “Ni foam-immobilized MIL-101(Cr)nanocrystals toward system integration for hydrogen strage”, J. AlloysComp., 2015, 645, S170-S173.

SUMMARY OF THE INVENTION

In each of Non Patent Literatures 1 to 4, a shaping technique forintroducing a PCP in a carrier has been disclosed, however, in any case,it has been difficult to carry the PCP to a carrier with a high fillingrate while maintaining the properties of the PCP.

That is, in each of Non Patent Literatures 3 and 4, there is adescription that the PCP is introduced at a relatively high introductionrate, however, in these literatures, the PCP is carried on a carrier byusing a binder. In general, since a binder tends to degrade theproperties of a PCP, it is difficult to carry the PCP on a carrier whilemaintaining the properties of the PCP by the methods of theseliteratures. Further, in each of Non Patent Literature 1 and 2, the PCPis carried on a silica monolith that is a silane-based carrier withoutusing a binder. However, the silica monolith in each of theseliteratures is obtained by polymerizing a tetrafunctional alkoxysilane,and due to the limitation of structure or physical properties of thecarrier, it has been difficult to highly fill the inside of the carrierwith the PCP.

On the other hand, in Patent Literature 1, there is a description thatmetal ions are adsorbed onto a so-called marshmallow-like gel that is acopolymer of a bi- or more-functional alkoxysilane, however, there is nodescription about carrying a PCP on the marshmallow-like gel.

An object of the present invention to provide a composite material onwhich a porous coordination polymer compound is carried with a highfilling rate in a state that the properties of the porous coordinationpolymer compound are maintained or improved, a gas adsorbent, and amethod for producing a composite material.

Solution to Problem

As a result of the intensive study to solve the problem described above,the present inventors have found that by using a marshmallow-like gel asa carrier of a PCP, the PCP can be carried on the carrier with a highfilling rate in a state that the properties of the PCP are maintained orimproved, and thus have completed the present invention.

That is, the present invention is a composite material, including aporous body having pores inside the porous body, and a porouscoordination polymer compound, and is characterized in that the porousbody has a network structure of Si—O bonds obtained by copolymerizing adialkoxysilane and a trialkoxysilane, and the porous coordinationpolymer compound is carried in the pores of the porous body.

The porous body preferably has a void ratio of 50% by volume or more.

Further, the pores of the porous body preferably have an average porediameter of 5 μm or more and 20 μm or less.

Furthermore, the ratio of a volume of the composite material to a volumeof the porous body is preferably 1.0 or less.

Moreover, the complex introduction rate indicated by a mass of theporous coordination polymer compound to the total mass of the compositematerial is preferably 40% by mass or more.

In addition, the porous body preferably has partial structuresrepresented by the following formulas (M1) and (M2):

(in the formula, A₁ is a functional group selected from the groupconsisting of a vinyl group, a cyano group, an alkyl group having 1 to 5carbon atoms, an amino group, a mercapto group, a fluoro group, an arylgroup, and an epoxy group; A₂ and A₃ are functional groups selected fromthe group consisting of a vinyl group, a cyano group, an alkyl grouphaving 1 to 5 carbon atoms, an amino group, a mercapto group, a fluorogroup, an aryl group, and an epoxy group, and may be the same as ordifferent from each other; and the symbol “*” represents a chemical bondand means to bond to adjacent Si.)

Further, the formula (M1) is preferably one or more kinds selected fromthe group consisting of the following formulas (M1-1), (M1-2), and(M1-3):

(in the formula, the symbol “*” represents a chemical bond and means tobond to adjacent Si.)

Furthermore, the formula (M2) is preferably one or more kinds selectedfrom the group consisting of the following formulas (M2-1), (M2-2), and(M2-3):

(in the formula, the symbol “*” represents a chemical bond and means tobond to adjacent Si.)

In addition, it is suitable that the porous coordination polymercompound has a structure in which an organic ligand is coordinated to ametal ion, the metal ion is a divalent to tetravalent metal ion, and theorganic ligand is a compound having a carboxyl group, a pyridyl group,or an imidazole group.

Further, the porous coordination polymer compound is preferably a porouscoordination polymer compound containing a divalent to tetravalent metalion and a divalent aromatic carboxylic acid having two COOH groups atmeta positions.

Furthermore, the porous coordination polymer compound preferably has astructure represented by the following formula (P1):

[Chemical formula 4]

{M(OOC—Y₁—COO)}₂   (P1)

(in the formula, M is a divalent, trivalent, or tetravalent metal ionselected from the group consisting of Cu²⁺, Zn²⁺, Ru²⁺, Rh²⁺, Mo²⁺,Fe³⁺, Al³⁺, Ti⁴⁺, and Co³⁺; and Y₁ represents a divalent aromatic grouphaving adjacent two COOH groups at meta positions.)

The present invention is a gas adsorbent that is characterized byincluding the composite material described in any one of the above.

In addition, the present invention is a method for producing a compositematerial containing a porous body having pores inside the porous bodyand a porous coordination polymer compound, and is characterized in thatthe porous body has a network structure of Si—O bonds obtained bycopolymerizing a dialkoxysilane and a trialkoxysilane, and the porouscoordination polymer compound is carried in the pores of the porous bodyvia a solvent.

Further, the method for producing a composite material preferablyincludes a washing step of removing the porous coordination polymercompound that has not been carried on the porous body after the porouscoordination polymer compound is brought into contact with the porousbody, and a drying step of drying the solvent.

Moreover, the solvent suitably has a property of swelling the porousbody.

In this case, the solvent is preferably at least one kind selected fromthe group consisting of methanol, ethanol, 1-propanol, 2-propanol,1-butanol, 2-butanol, benzene, hexane, acetaldehyde, acetone,cyclohexane, and N,N-dimethylformamide.

In addition, it is preferred that the porous body has partial structuresrepresented by the following formulas (M1) and (M2):

(in the formula, A₁ is a functional group selected from the groupconsisting of a vinyl group, a cyano group, an alkyl group having 1 to 5carbon atoms, an amino group, a mercapto group, a fluoro group, an arylgroup, and an epoxy group; A₂ and A₃ are functional groups selected fromthe group consisting of a vinyl group, a cyano group, an alkyl grouphaving 1 to 5 carbon atoms, an amino group, a mercapto group, a fluorogroup, an aryl group, and an epoxy group, and may be the same as ordifferent from each other; and the symbol “*” represents a chemical bondand means to bond to adjacent Si.),

and is produced by copolymerizing a compound represented by thefollowing formula (M3) with a compound represented by the followingformula (M4):

(in the formula, R₁ to R₅ each are an alkyl group having 1 to 5 carbonatoms and may be the same as or different from each other, and A₁ to A₃are the same as the above.)

Further, the method for producing a composite material suitably includesa dispersion liquid adjustment step of adjusting a dispersion liquid ofa porous coordination polymer compound by dispersing the porouscoordination polymer compound in the solvent, and a contact step ofbringing the dispersion liquid into contact with the porous body tointroduce the porous coordination polymer compound into the pores aresuitably included.

Furthermore, in the contact step, the porous body is preferably broughtinto contact with the dispersion liquid while being swelled.

Moreover, the method for producing a composite material preferablyincludes a drying step of removing the solvent from the porous bodyafter the contact step.

In addition, in these cases, in the contact step, when a volume of theporous body before the contact is taken as V0 and a volume of the porousbody after the contact is taken as V1, a volume expansion rate (V1/V0)of the porous body is preferably in a range of 1.2 to 2.0.

Further, the present invention is a method for producing a compositematerial containing a porous body having pores inside the porous bodyand a porous coordination polymer compound, and is characterized in thatthe porous coordination polymer compound is carried in the pores of theporous body via a solvent.

In this case, the method for producing a composite material preferablyincludes a dispersion liquid adjustment step of adjusting a dispersionliquid of a porous coordination polymer compound by dispersing theporous coordination polymer compound in the solvent, and a contact stepof bringing the dispersion liquid into contact with the porous body tointroduce the porous coordination polymer compound into the pores.

Advantageous Effects of Invention

According to the present invention, a composite material on which aporous coordination polymer compound is carried with a high filling ratein a state that the properties of the porous coordination polymercompound are maintained or improved, a gas adsorbent, and a method forproducing a composite material can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is SEM images of a porous body and a composite material ofExamples.

FIG. 2 is an enlarged photograph on a surface of a porous body.

FIG. 3 is a graph showing results of the CO adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

FIG. 4 is a graph showing results of the CO adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

FIG. 5 is a graph showing results of X-ray diffraction of compositematerials of Examples.

FIG. 6 is a graph showing results of the load characteristics evaluationconducted by using composite materials of Examples.

FIG. 7 is a graph showing results of the CO₂ adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

FIG. 8 is a graph showing results of the CO₂ adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

FIG. 9 is a graph showing results of the CO₂ adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

FIG. 10 is a graph showing results of the CO₂ adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

FIG. 11 is a graph showing results of the CO₂ adsorption/desorptionisotherm measurement conducted by using composite materials of Examples.

DESCRIPTION OF THE INVENTION 1. Composite Material

Hereinafter, the composite material according to the present inventionwill be described. The composite material according to the presentinvention is a material obtained by combining a porous body having poresinside the porous body and a porous coordination polymer compound. Theporous body has a network structure of Si-bonds obtained bycopolymerizing a dialkoxysilane and a trialkoxysilane, and the porouscoordination polymer compound is carried in the pores of the porousbody. Hereinafter, each member will be described in detail.

(1) Porous Coordination Polymer Compound

The porous coordination polymer compound is a porous compound havingnanopores in which metal ions and organic ligands form athree-dimensional coordination network. In more detail, the porouscoordination polymer compound is a porous material in which acrystalline polymer structure having spaces (nanopores) inside thestructure is formed by combining various metal ions and crosslinkableorganic ligands that connect the metal ions, and has an internal spaceformed by assembling crystals while the crystals are grownthree-dimensionally. Note that in the present specification, the porouscoordination polymer compound may be simply referred to as “PCP”.

Metal Ion

As the metal ion constituting a porous coordination polymer compound,any metal ion may be used as long as it can form a porous material bycombining with an organic ligand. As such a metal ion, a transitionmetal can be used. Specific examples of the metal ion include variouskinds of ions of nickel, copper, zinc, ruthenium, rhodium, molybdenum,chromium, iron, titanium, zirconium, and the like. Hexavalent molybdenumand hexavalent chromium may be accepted. As a specific example of themetal suitably used in the present invention, a divalent orhigher-valent metal ion, and preferably a divalent to tetravalent metalion can be mentioned. Specific examples of the metal ion described aboveinclude a nickel ion (Ni²⁺), a copper ion (Cu²⁺), a zinc ion (Zn²⁺), aruthenium ion (Ru²⁺), a rhodium ion (Rh²⁺), a molybdenum ion (Mo²⁺), acobalt ion (Co²⁺, Co³⁺), a chromium ion (Cr³⁺), an iron ion (Fe²⁺,Fe³⁺), a titanium ion (Ti⁴⁺), a zirconium ion (Zr⁴⁺), and an aluminumion (Al³⁺).

In selecting the metal ion, taking the ease of production of the porouscoordination polymer compound, the stability, the application and thelike into consideration, and further taking the ease of theincorporation into the porous substance of the present invention, thestability of adsorption characteristics and the like into considerationin the present invention, the selection is performed. When such aconsideration is taken, copper, zirconium, chromium, and the like can bementioned, and from the viewpoint of the ease of the combination and thelike, it is more preferred to use copper, zirconium or the like inrelation to the porous substance.

Organic Ligand

As the organic ligand constituting a porous coordination polymercompound, any organic ligand may be used as long as it can form a porousmaterial by combining with a metal ion, and an oxygen donor ligand, anitrogen donor ligand, and the like can be mentioned. Further, as thekind of the organic ligand, any of a monodentate ligand, and amultidentate ligand (bidentate ligand or tridentate or higher ligand)may be used.

As the oxygen donor ligand, a compound having a carboxyl group, such asan aromatic carboxylic acid, and an aliphatic carboxylic acid can bementioned. As the compound having a carboxyl group, a compound havingtwo or more carboxyl groups in the molecule is preferred, and inparticular, a compound having at least one unsaturated carbon-carbonbond between two carboxyl groups (that is a double bond or a triplebond, and may be a single bond or a ring structure such as a benzenering or a heterocyclic ring) is preferred.

Specific examples of the aromatic carboxylic acid include abenzenedicarboxylic acid such as phthalic acid, isophthalic acid, andterephthalic acid, and a benzenetricarboxylic acid such as1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, and1,3,5-benzenetricarboxylic acid. Further, specific examples of thealiphatic carboxylic acid include fumaric acid, and maleic acid.

In particular, as the benzenedicarboxylic acid, compounds represented bythe following formulas (L1) to (L6) are preferred.

(in the formula, R11 to R52 each are selected from the group consistingof a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, anamino group (NH₂), an amide group (CONH₂), an azido group (N₃), anacetylamino group, a nitro group, and a halogen atom, these may bereplaced with a substituent and/or a halogen atom, and R11 to R52 may bethe same as or different from each other.)

In this regard, examples of the alkyl group include a linear or branchedalkyl group having 1 to 4 carbon atoms such as a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, and a tert-butyl group. Further,examples of the aryl group include a phenyl group, and a naphthyl group.In addition, examples of the alkoxy group include a linear or branchedalkoxy group having 1 to 4 carbon atoms such as a methoxy group, anethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxygroup, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.Further, examples of the halogen atom include a chlorine atom, afluorine atom, a bromine atom, and an iodine atom.

These may partially contain an unsaturated bond (double bond, or triplebond). Further, these may be partially replaced with a substituent or ahalogen atom. Examples of the substituent include an alkyl group, anaryl group, an alkoxy group, and an amino group, and examples of thehalogen atom include a chlorine atom, a fluorine atom, a bromine atom,and an iodine atom. In addition, in formulas L1 to L6, the number ofsubstituents (R) in one molecule is 1 to 4, preferably 1 to 3, morepreferably 1 or 2, and particularly 1.

In a case where the benzenedicarboxylic acid is isophthalic acid offormula L1, one having a substituent at the 5-position is preferred, andfor example, 5-azidoisophthalic acid, 5-methylisophthalic acid,5-methoxyisophthalic acid, 5-heptafluoropropyl isophthalic acid, and thelike can be mentioned.

As the nitrogen donor ligand, a compound having two or more pyridylgroups in the molecule, or a compound having an imidazole group can bementioned. As such a compound, 4,4′-bipyridine, imidazole,phenanthroline, and the like can be mentioned.

Coordination Structure Between Metal Ion and Organic Ligand

It is preferred that the porous coordination polymer compound has astructure in which an organic ligand is coordinated to a metal ion, themetal ion is a divalent to tetravalent metal ion, and the organic ligandis a compound having a carboxyl group, a pyridyl group, or an imidazolegroup. The porous coordination polymer compound has a structure in which1 or 2 or more organic ligands are coordinated centering around theabove-described metal ion. The coordination structure may be any of alinear shape, a planar square shape, a regular tetrahedron shape, aregular octahedron shape, and the like.

In particular, as the porous coordination polymer compound, one having abinuclear metal cluster structure in which an aromatic carboxylic acidis coordinated to a divalent metal ion is preferred. In this case, onehaving a structure represented by the following formula (P1) isparticularly preferred.

[Chemical formula 8]

{M(OOC—Y₁—COO)}₂   (P1)

(a nickel ion (Ni²⁺), a copper ion (Cu²⁺), a zinc ion (Zn²⁺), aruthenium ion (Ru²⁺), a rhodium ion (Rh²⁺), a molybdenum ion (Mo²⁺), acobalt ion (Co²⁺, Co³⁺), a chromium ion (Cr³⁺), an iron ion (Fe²⁺,Fe³⁺), a titanium ion (Ti⁴⁺), a zirconium ion (Zr⁴⁺), and an aluminumion (Al³⁺), and Y₁ represents a divalent or trivalent aromatic grouphaving adjacent two COOH groups at meta positions.)

In selecting the ligand of the present invention, there is no particularlimitation, and one that is easily incorporated into the porous body ofthe present invention and is easily adsorbed is preferred. In a casewhere the particle size of the porous coordination polymer compound isexcessively large or the dispersibility is poor when the porouscoordination polymer compound is incorporated into the porous body, dueto the selected ligand, favorable results may not be obtained in somecases. It is important to use the above-described ligand in order toobtain the effects of the present invention.

Shape of Porous Coordination Polymer Compound

The shape of the porous coordination polymer compound is notparticularly limited, and a particle shape is preferred. In this case,the average particle diameter of the porous coordination polymercompound is generally 0.01 to 100 μm, and preferably 0.1 to 50 μm. In acase where the average particle diameter of the porous coordinationpolymer compound is within the above-described range, the particlediameter becomes appropriate, the handling tends to be easy, and theporous coordination polymer compound is easily introduced into pores ofa porous body, and further, since aggregation of particles, or the likeis hardly generated, the dispersibility in a solvent or the like isimproved. (In a case where the average particle diameter is less than0.01 μm, the particles are extremely small, the handleability becomesdifficult, and the particles are hardly dispersed in a solvent or thelike due to the aggregation of the particles, or the like. In a casewhere the average particle diameter of the porous coordination polymercompound exceeds 100 μm, the particles are extremely large, and arehardly introduced into pores of a porous body.) The average particlesystem can be controlled by appropriately changing the combination ofthe ligand and the metal, which are the raw materials for producing theporous coordination polymer compound.

Method for Producing Porous Coordination Polymer Compound

The porous coordination polymer compound of the present invention may beobtained only by mixing a metal ion of the above-described metalelement, an organic ligand, a solvent, and a base as needed, andstirring the resultant mixture, but the mixture may be placed in apressure resistant container such as an autoclave, and reacted underpressure at high temperature.

The metal ion can be supplied into the reaction mixture by adding ametal compound soluble in a solvent to a reaction solvent. As such ametal compound, a metal sulfate, a metal acetate, a metal nitrate, ametal chloride, a metal bromide, a metal iodide, a metal perchlorate, ora metal hydroxide can be mentioned, and specifically, copper nitrate,copper acetate, copper perchlorate, or the like can be mentioned.

Further, in a case where the organic ligand is a compound having acarboxyl group, the carboxyl group may be reacted as it is in an acidstate (COOH), or may be reacted in an alkali metal salt state (COONa,COOK, COOLi, or the like).

The concentration of the metal ion in reaction of the metal ion and anorganic ligand is around 1 to 1000 mM (mmol/l), and the concentration ofthe organic ligand is around 1 to 2000 mM.

As the mixture ratio of the metal ion and the organic ligand, the molarratio of the metal cation to the coordination bond group of the organicligand is preferably around 1:1, and in the ratio, either one may beused excessively or largely excessively.

Into a reaction system of the metal ion and the organic ligand, a basemay be added as needed. Since a base has a function of promotingdeprotonation of a ligand, the addition of a base is preferred from theviewpoint of improving the reactivity. Examples of the base include aninorganic base, and an organic base. Examples of the inorganic baseinclude lithium hydroxide, sodium carbonate, potassium carbonate, sodiumhydroxide, and potassium hydroxide. Examples of the organic base includetriethylamine, diethylisopropylamine, pyridine, and 2,6-lutidine. Amongthem, from the viewpoint of the reaction acceleration, pyridine, lithiumhydroxide, or sodium carbonate is preferred. The amount of the base tobe added is 0.01 to 10 moles of base, and is preferably 0.05 to 5 moles,relative to 1 mole of the organic ligand.

The reaction temperature of the metal ion and the organic ligand isusually an ordinary temperature (25° C.) to 300° C., and is morepreferably 250° C. or less. This is because the reaction proceedssufficiently and the decomposition of a product is hardly generated in acase where the reaction temperature is within the above-described range.(In a case where the reaction temperature exceeds 300° C., a product maybe decomposed, and in a case where the reaction temperature is lowerthan 25° C., the reaction hardly proceeds.)

The time and temperature of the reaction between the metal ion and theorganic ligand can be appropriately set according to the scale ofsynthesis, and as the temperature is lower, it takes a longer time, andin general, the time is 30 minutes to 3 weeks. When the reaction isperformed with a homogeneous solvent, the reaction time is aroundseveral hours, and this is not a problem, but in a case where thereaction is performed in a pressure resistant container underheterogeneous conditions, it may take a long time, specifically aroundone week in some cases. The reaction pressure is from normal pressure to1 to 10 MPa, and preferably around 3 to 5 MPa.

In order to promote the synthesis reaction of the porous coordinationpolymer compound, a small amount of an acid such as hydrofluoric acid,hydrochloric acid, formic acid, acetic acid, and nitric acid, or analkali such as sodium hydroxide may be added to the reaction solvent.Since an acid or an alkali interferes with the synthesis of the porouscoordination polymer compound when used in a large amount, the amount isaround 0.1 to 10 times mol, and preferably around 1 to 5 times mol tothe amount of the ligand.

As the solvent to be used for a reaction between the metal ion and theorganic ligand, any one of water, acetone, alcohols such as methanol andethanol, and an organic solvent such as acetonitrile, tetrahydrofuran,dioxane, dimethylformamide, dimethylacetamide, toluene, and hexane maybe used, and these solvents may be used alone or in combination thereof.The amount of the solvent to be used is not particularly limited, and ispreferably around 10 to 2000 times the total mass of the metal ion andthe organic ligand on a mass basis from the viewpoint of the ease ofreaction control.

After completion of the reaction between the metal ion and the organicligand, the product can be easily isolated by performing filtration andcentrifugation of the precipitate. After the product isolation, theisolated product is washed with water or an organic solvent as needed.In order to use the isolated product as an adsorbent, it is particularlypreferred to remove the solvent by rapidly heating the isolated productunder reduced pressure. By removing the solvent, there is a tendencythat the porous coordination polymer compound is stabilized and theporous structure is maintained. The heating temperature is suitablyaround 50 to 200° C. In this regard, when the obtained product is leftfor a long period of time, for example, several days without removingthe solvent, the crystal structure of the porous coordination polymercompound changes and the specific surface area decreases, as a result ofwhich the performance as an adsorbent or a catalyst may be impaired insome cases.

Application of Porous Coordination Polymer Compound

The porous coordination polymer compound has various characteristics bythe combination of the metal ion and the organic ligand. The porouscoordination polymer compound can be suitably used particularly as a gasseparation element. Examples of the gas include carbon dioxide,hydrogen, carbon monoxide, oxygen, nitrogen, a hydrocarbon having 1 to 4carbon atoms (such as methane, ethane, ethylene, or acetylene), a raregas (such as helium, neon, argon, krypton, or xenon), hydrogen sulfide,ammonia, a sulfur oxide (such as SO2), a nitrogen oxide (such as NO,NO₂, N₂O₄, or N₂O), a siloxane (such as hexamethylcyclotrisiloxane, oroctamethylcyclotetrasiloxane), water vapor, and organic steam. Amongthem, particularly carbon monoxide (CO) can be separated efficiently.

(2) Porous Body

In the porous body of the present invention, the network structure ofSi—O bonds obtained by copolymerizing a dialkoxysilane and atrialkoxysilane has a three-dimensionally randomly connected structurein at least a part of the network structure. The network structure haspores in the inside of the network structure.

The dialkoxysilane is a silane compound in which two alkoxy groups (—OR)are bonded to silicon and two functional groups are bonded. Further, thetrialkoxysilane is a silane compound in which three alkoxy groups arebonded to silicon and one functional group is bonded. The porous body ofthe present invention has a three-dimensional structure by a network ofSi—O bonds between the dialkoxysilanes, between the trialkoxysilanes,and between the dialkoxysilane and the trialkoxysilane.

When a surface of the porous body is observed with an opticalmicroscope, as shown in FIG. 2, an open structure as if the structurehas holes may be observed in some cases. The diameter of the openstructure on a surface of the porous body is not particularly limited aslong as a porous coordination polymer compound can be introduced intopores, and is generally 1 to 1000 μm and is 1 to 100 μm in some cases,and a case where the diameter is 5 to 20 μm is also observed. In thatcase, the porous body with a structure having a diameter of 700 to 1000μm (Example 3 of the present application) or even 300 to 400 μm onaverage can be used. From the view point of the space filling rate orthe introduction rate of the porous coordination polymer compound, thelatter is more advantageous (Examples 4 and 5 of the presentapplication). In particular, taking the ease of introduction of theporous coordination polymer compound into a porous body, the stabilityafter formation of a composite, or the like into consideration, it isfavorable that the diameter is not extremely large or not extremelysmall.

Pores are observed on a surface of the porous body. The average porediameter is not particularly limited as long as a porous coordinationpolymer compound can be introduced inside the pores, and the openingdiameter of each of the pores on a surface of the porous body ispreferably equal to or larger than the particle diameter of the porouscoordination polymer compound. The opening diameter is generally 1 μm ormore and preferably 5 μm or more, and is usually 100 μm or less andpreferably 20 μm or less. Further, the range of the average porediameter is not particularly limited, and is 1 to 100 μm and preferably5 to 20 μm.

In a case where the average pore diameter of the porous body is withinthe above-described range, it becomes easy to introduce a porouscoordination polymer compound into the pores, and further, the porouscoordination polymer compound introduced into the pores hardly leaks tothe outside. In particular, the average pore diameter of the porous bodyis preferably equal to or larger than the particle diameter of theporous coordination polymer compound. The smaller the average porediameter of the porous body is as compared with the particle diameter ofthe porous coordination polymer compound, the easier it is to introducethe porous coordination polymer compound into the pores. Conversely, thecloser the average pore diameter of the porous body is to the particlediameter of the porous coordination polymer compound, the more difficultit is for the porous coordination polymer compound introduced once intothe pores to flow to the outside.

The electron micrograph of FIG. 1 shows the state of the porous body ofthe present invention. Ones observed to be spherical are porous organicsilica structures constituting the porous body of the present invention,and the porous body of the present invention is formed by assemblingporous organic silica structures. The part where porous organic silicastructures are not assembled is a pore. The present inventors, et al. donot take a specific theory on the state in which the porous coordinationpolymer compound is adsorbed to a porous body, however, it can bedescribed that the central part of the porous coordination polymercompound (the photograph in the upper part of FIG. 1), which is a partwhere porous organic silica structures are not assembled, is a pore, andwhen the porous coordination polymer compound is incorporated in thepores, the porous coordination polymer compound is physically andchemically incorporated and adsorbed in the porous body.

In this regard, the values of the opening diameter and the average porediameter in the present specification are the results obtained by themeasurement with the method described in Examples to be described later,and specifically, are the values determined by specifying pore partsfrom an electron microscope (SEM) image of the porous body, and takingthe length distribution in the major axis direction when the pore partseach are assumed to be an oval shape.

The theoretical maximum introduction rate of a PCP to the porous body ispreferably 60% by mass or more, and more preferably 70% by mass or more.Further, the upper limit of the theoretical maximum introduction rate ofa PCP to the porous body is not particularly limited, and is usually 99%by mass or less and 95% by mass or less. In this regard, the theoreticalmaximum introduction rate is a theoretical value of the maximum value ofa PCP that can be introduced into pores of the porous body, and it canbe expected that the larger the value is, the larger the amount of a PCPthat can be introduced into the porous body is. The value of thetheoretical maximum introduction rate in the present specification isthe result obtained by the measurement with the method described inExamples to be described later, and specifically, is the valuecalculated by using the following equation.

V _(pore)×ρ_(PCP) =M _(PCPMAX)

Theoretical maximum introduction rate=(M _(PCPMAX)/(M _(porous) +M_(PCPMAX)))×100   Equation

(where V_(pore): void volume of a porous body, ρ_(PCP): bulk density ofa PCP, M_(PCPMAX): theoretical maximum mass of a PCP occupying void,M_(porous): mass of a porous body, and further, at this time, ρ_(PCP) isobtained by putting 1 g of PCP in a graduated cylinder, tapping on thePCP with a weight of 100 g to fill the graduated cylinder with the PCP,and measuring the volume.)

A porous body has voids due to the three-dimensional structure by anetwork, and a porous coordination polymer compound can be introducedinto the inside of the porous body. The void ratio of the porous body is50% by volume or more, preferably 70% by volume or more, and morepreferably 60% by volume or more. As the void ratio of the porous bodyis higher, it is easier to introduce the porous coordination polymercompound in more amount into the pores. Further, the upper limit of thevoid ratio of the porous body is not particularly limited, and isusually 99% by volume or less and 95% by volume or less. In this regard,the void ratio means a ratio of the volume of the pores to the totalvolume of the porous body. Further, the value of the void ratio in thepresent specification is the result obtained by the measurement with themethod described in Examples to be described later, and specifically, isthe value calculated from the ratio obtained by taking the increasedvolume of a solution when the porous body is immersed in methanol (99%)as the skeletal volume of a porous body, and taking the difference fromthe volume of the porous body as the void volume.

The network structure of the porous body of the present inventionpreferably has partial structures represented by the following formulas(M1) and (M2).

(in the formula, A₁ is a functional group selected from the groupconsisting of a vinyl group, a cyano group, an alkyl group having 1 to 5carbon atoms, an amino group, a mercapto group, a fluoro group, an arylgroup, and an epoxy group; A₂ and A₃ are functional groups selected fromthe group consisting of a vinyl group, a cyano group, an alkyl grouphaving 1 to 5 carbon atoms, an amino group, a mercapto group, a fluorogroup, an aryl group, and an epoxy group, and may be the same as ordifferent from each other; and the symbol “*” represents a chemical bondand means to bond to adjacent Si.)

The combination of the formula (M1) and the formula (M2) can be used bythe appropriate and arbitrary combination within the range that theeffects of the present invention are obtained. The network structure ofthe porous body of the present invention is characterized by having arandom and flexible structure but not a lattice structure, and theadjustment of the randomness can be performed by the selection of A1,A2, and A3 taking the chemical properties, the length of substituent,the bulk height, and the like into consideration. Therefore, the sizesand properties of the openings and pores present on a surface of theporous body can be controlled. As a result, the influences on the spacefilling rate and on the introduction rate of the porous coordinationpolymer compound can be exerted.

In particular, the formula (M1) is preferably one or more kinds selectedfrom the group consisting of the following formulas (M1-1), (M1-2), and(M1-3).

(in the formula, the symbol “*” represents a chemical bond and means tobond to adjacent Si.)

Further, the formula (M2) is preferably one or more kinds selected fromthe group consisting of the following formulas (M2-1), (M2-2), and(M2-3).

(in the formula, the symbol “*” represents a chemical bond and means tobond to adjacent Si.)

The porous body of the present invention may partially have anotherstructure as long as it has a network structure obtained bycopolymerizing a dialkoxysilane and a trialkoxysilane. As such astructure, for example, a structure in which a tetraalkoxysilane havingfour alkoxy groups is used as a basic skeleton, or the like can bementioned. Examples of the tetraalkoxysilane include tetramethoxysilane,and tetraethoxysilane.

The network structure obtained by copolymerizing a dialkoxysilane and atrialkoxysilane is contained in an amount of preferably 80 mol % ormore, more preferably 90 mol % or more, and particularly preferably 99mol % or more, relative to the entire porous body.

Method for Producing Porous Body

A porous body can be produced by copolymerizing a dialkoxysilane and atrialkoxysilane. In this regard, in the above copolymerization, acomponent other than the dialkoxysilane and the trialkoxysilane may becontained.

The copolymerization of a dialkoxysilane and a trialkoxysilane can beperformed by a known method, and for example, the copolymerization canbe performed by adding a dialkoxysilane and a trialkoxysilane to anacidic solution containing a surfactant and a hydrolyzable compound toform a sol and then aging the sol for a long period of time at hightemperature to turn the sol into a gel. Hereinafter, the productionmethod will be described in detail.

As the dialkoxysilane to be a raw material, any dialkoxysilane can beappropriately selected depending on the physical properties or the liketo be required for the porous body as long as it has two alkoxy groups.Similarly, as the trialkoxysilane to be a raw material, anytrialkoxysilane can be appropriately selected depending on the physicalproperties or the like to be required for the porous body as long as ithas three alkoxy groups.

In particular, the porous body having partial structures represented bythe above formulas (M1) and (M2) can be produced by copolymerizing atrialkoxysilane represented by the following formula (M3) and adialkoxysilane represented by the following formula (M4).

(in the formula, R₁ to R₅ each are an alkyl group having 1 to 5 carbonatoms and may be the same as or different from each other, and A₁ to A₃are the same as the above.)

In particular, since the porous body to be obtained has a high voidratio and is excellent in the flexibility, as the dialkoxysilane, one ormore compounds selected from the group consisting ofdimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane,vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane are preferred.Further, as the trialkoxysilane to be copolymerized with the above oneor more compounds, for example, one or more compounds selected from thegroup consisting of methyltrimethoxysilane, ethyltrimethoxysilane,methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and4-(trimethoxysilyl)butane nitrile are preferred.

With respect to the dialkoxysilane and the trialkoxysilane, thecompounds of each of the dialkoxysilane and the trialkoxysilane may beused singly alone, or in combination of two or more kinds thereof. Forexample, one kind of a dialkoxysilane and two kinds of trialkoxysilanesmay be used, or two kinds of dialkoxysilanes and one kind of atrialkoxysilane may be used.

The mixing amount of a dialkoxysilane and a trialkoxysilane can beappropriately set depending on the characteristics or the like to berequired for the porous body, and is generally 1:10 to 10:1 andpreferably 1:5 to 5:1 in terms of a molar ratio. Further, in a casewhere two or more kinds of either one or both of the dialkoxysilanes andthe trialkoxysilanes are used, the mixing amount is generally 1:10 to10:1 and preferably 1:5 to 5:1 in terms of a molar ratio relative to thetotal amount of the dialkoxysilanes and the total amount of thetrialkoxysilanes.

In addition, as described above, the porous body may partially have astructure other than the network structure obtained by copolymerizing adialkoxysilane and a trialkoxysilane. In a case where the porous bodyhas such another structure, for example, a tetraalkoxysilane such astetramethoxysilane, and tetraethoxysilane may be added. The content ofthe tetraalkoxysilane is preferably 1% by mass or less, and morepreferably 0.5% by mass or less, relative to the total weight of thewhole monomers including the dialkoxysilane and the trialkoxysilane.When the content of the tetraalkoxysilane exceeds 1% by mass, synthesisof the porous body tends to be difficult.

Next, by using an acidic solution, the dialkoxysilane and thetrialkoxysilane are hydrolyzed to turn the silicon compound into a sol.In this process, the alkoxy groups of the dialkoxysilane and thetrialkoxysilane form a siloxane network by the hydrolysis and thepolycondensation reaction, and the non-hydrolyzable functional groupother than the alkoxy group is not hydrolyzed and is maintained.

As the acid of the acidic solution, carboxylic acids can be mentioned,for example, acetic acid, formic acid, propionic acid, oxalic acid, ormalonic acid is preferred, and acetic acid is more preferred. Theconcentration of the acidic solution is not particularly limited as longas it is a concentration at which the hydrolysis reaction proceeds, andthe concentration is generally 0.1 to 200 mM (mmol/l), and preferably 2to 50 mM.

A surfactant has a function of reducing the difference in chemicalaffinity between a solvent and a copolymer in a reaction system, and byreducing the difference, pores of a porous body become finer. As thesurfactant, a nonionic surfactant, or an ionic surfactant can bementioned, and an ionic surfactant is preferred, and a cationicsurfactant is more preferred. As the cationic surfactant,hexadecyltrimethylammonium chloride, or hexadecyltrimethylammoniumbromide can be mentioned, and among them, hexadecyltrimethylammoniumchloride is preferred because of having a high affinity. The amount ofthe surfactant is generally 0.001 to 1% by mass, and preferably 0.01 to0.1% by mass, relative to the total mass of the acidic solutioncontaining a dialkoxysilane, a trialkoxysilane, a surfactant, and ahydrolyzable compound.

The hydrolyzable compound has a function of promoting the gelation of asol being formed. Examples of the hydrolyzable compound include urea,formamide, N-methylformamide, N,N-dimethylformamide, acetamide,N-methylacetamide, N,N-dimethylacetamide, and hexamethylenetetramine,and among them, urea having a high effect of promoting the gelation ispreferred. The amount of the hydrolyzable compound is generally 0.01 to10% by mass, and is preferably 0.1 to 1.0% by mass, relative to thetotal mass of the acidic solution containing a dialkoxysilane, atrialkoxysilane, a surfactant, and a hydrolyzable compound.

The solation temperature is not particularly limited as long as it is atemperature at which the hydrolysis reaction proceeds, and is generally10 to 50° C., and preferably 20 to 40° C. Further, although depending onthe reaction conditions, the solation time is generally 10 minutes to 5hours, and preferably 30 minutes to 2 hours.

Gelation of the obtained sol is conducted by aging. The aging can beconducted by leaving the sol that is a reactant to stand. The gelationtemperature (aging temperature) is not particularly limited as long asit is a temperature at which the sol turns into a gel, and is generally50 to 200° C., and preferably to 100° C. Further, although depending onthe reaction conditions, the gelation time (aging time) is generally 1to 50 hours, and preferably 15 to 20 hours.

Next, in order to remove the moisture, acidic solution, surfactant,hydrolyzable compound, unreacted silicon compound material and the like,which remain in the gel obtained by sol-gel reaction, it is preferred toperform solvent exchange by using an organic polar solvent. Through theprocesses described above, a network of a flexible gel can beconstructed by the networking of Si—O bonds.

The porous body can be formed into a desired shape by putting the porousbody into a mold having a specific shape, and conducting sol-gelreaction so that the porous body is molded, or by conducting sol-gelreaction as it is unmolded and then cutting the resultant product into aspecific shape, or the like. As the shape of the porous body, aspherical shape, a cylindrical shape, a conical shape, a square shape, aprismatic pillar shape, a pyramid shape, or the like can be used.

2. Method for Producing Composite Material (Combining Method)

Next, the method for producing a composite material according to thepresent invention will be described. The composite material can beproduced by preparing a porous body having a network structure of Si—Obonds obtained by copolymerizing a dialkoxysilane and a trialkoxysilane,and by carrying a porous coordination polymer compound in pores of theporous body via a solvent.

There are roughly two methods for producing a composite material. One isa method in which a PCP is synthesized in advance separately from aporous body, and the synthesized PCP is brought into contact with theporous body so as to be carried on the porous body (hereinafter, alsoreferred to as “external synthesis method”). The other is a method inwhich a synthesis reaction of a PCP is performed inside the pores of aporous body, and the synthesized PCP comes into contact with the porousbody and is carried on the porous body (hereinafter, also referred to as“internal synthesis method”). The production method according to thepresent invention includes both of the external synthesis method and theinternal synthesis method.

External Synthesis Method

Hereinafter, the external synthesis method will be described. In theexternal synthesis method, at first, a porous body and a porouscoordination polymer compound are separately adjusted. These can beproduced by the method described in the section of “(Method forproducing porous body)”, and the section of “(Method for producingporous coordination polymer compound)”. Note that the method forproducing a composite material by the external synthesis method is apreferred method for producing the composite material according to thepresent invention. That is, taking the versatility and the productioncost into consideration, the external synthesis method is superior to aninternal synthesis method to be described later. As compared with aninternal synthesis method, the external synthesis method can reduce theamount of a reagent to be used during synthesis, the loss is large, andit is easier to introduce a PCP homogeneously as compared with aninternal synthesis method, and further it is advantageous in attachingthe PCP to the inside of a shaping material. From these points of view,as the method for producing a composite material, the external synthesismethod is preferable to the internal synthesis method.

Next, the porous coordination polymer compound is dispersed in a solventto adjust a dispersion liquid (dispersion liquid adjustment step). Asthe solvent, one that does not dissolve both of the porous body and theporous coordination polymer compound is selected. In this regard, theexpression “not dissolve both” means that no significant amount of bothof the porous body and the porous coordination polymer compounddissolves in a solvent. As described above, structurally, both of theporous coordination polymer compound and the porous body are thoseformed by three-dimensionally bonding molecules, and it can also be saidthat the solvent is a solvent that does not break the bond due to theaction of a solvent. With respect to the porous coordination polymercompound, as the solvent, there is also a meaning of not dissolving themetal ion in the porous coordination polymer compound into the solvent.

Further, as the solvent, a solvent having a property of swelling aporous body is preferred. Herein, the expression “swelling a porousbody” means that a solvent acts on a porous body so that the solvent isincorporated into the porous body, and the volume is increased bychanging a part or most of the intermolecular distances without changingthe basic structure.

A solvent having these characteristics can be appropriately selecteddepending on the properties of the porous coordination polymer compoundor the porous body. The solvent that can be selected may be a non-polarsolvent or a polar solvent, and may also be a protic solvent, or anaprotic solvent. Further, as the kind of the solvent, either an aqueoussolvent or an organic solvent may be used.

Specific examples of the solvent include water as an aqueous solvent,and as an organic solvent, an alcohol having 1 to 10 carbon atoms, analdehyde having 1 to 5 carbon atoms, a ketone having 3 to 5 carbonatoms, and a cyclic hydrocarbon having 5 to 10 carbon atoms. Morespecific examples of the organic solvent include methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 2-butanol, benzene, hexane,acetaldehyde, acetone, cyclohexane, and N,N-dimethylformamide. Thesesolvents may be used singly alone, or may be used by mixing two or morekinds thereof. Among them, methanol, ethanol, acetone, cyclohexane, andN,N-dimethylformamide are preferred from the viewpoint of the highpermeability into pores of a porous body, and in particular, methanol,ethanol, and acetone are preferred.

Subsequently, the dispersion liquid adjusted in the above is broughtinto contact with a porous body to introduce a porous coordinationpolymer compound into pores (contact step). The contact step can beperformed by bringing a porous body into contact with a dispersionliquid. In the contact step, it is preferred to perform the stirringlightly by using a stirrer or the like in a state that the porous bodyis brought into contact with the dispersion liquid. As the stirrer, astirrer having a rotor, or the like can be mentioned. In this regard, itis not necessary to perform the stirring strongly, but rather, it isimportant to pay attention so that particles of a porous coordinationpolymer compound are not broken due to the stirring or that the porouscoordination polymer compound incorporated into pores of the porous bodyis not discharged outside the pores. That is, it is sufficient to stirthe particles of the porous coordination polymer compound to such anextent that the particles are stirred up in a solvent, and it ispreferred to perform the stirring to such an extent that the porous bodyis not stirred up in the solvent.

In this regard, in the above-described embodiment, the contact step isperformed while the porous body is immersed in a dispersion liquid inwhich the porous coordination polymer compound is dispersed in asolvent, but the contact step is not limited thereto. As the contactstep, for example, a method in which a porous coordination polymercompound in a powder form is added to a porous body in a state that theporous body is immersed in a solvent in advance, a method in which aporous body and a porous coordination polymer compound in a powder formare mixed and then a solvent is added to the resultant mixture, or thelike may also be accepted.

Further, in a case where a solvent having a property of swelling aporous body is used as the solvent, the porous body swells in thecontact step. With respect to the swelling ratio at this time, when thevolume of the porous body before immersion is taken as V0 and the volumeafter immersion is taken as V1, a volume expansion rate (V1/V0) of theporous body is preferably in a range of 1.2 to 2.0, and more preferablyin a range of 1.3 to 1.7. As described above, when the porous bodyswells with a solvent, the porous coordination polymer compound easilyenters the pores of the porous body, and the filling rate of the porouscoordination polymer compound to the porous body can be increased.

Washing and Drying Steps

It is preferred to perform a washing step of removing a porouscoordination polymer compound that has not been carried on a porous bodyafter the porous coordination polymer compound is brought into contactwith the porous body, and a drying step of drying a solvent.

The washing step is a step of removing an unreacted porous coordinationpolymer compound and other components. The washing step is performed bya method of washing a composite material with a washing solvent.Examples of the washing solvent include water, and an organic solventsuch as ethanol or methanol. The washing may be performed only once, ormay be performed multiple times.

The drying step is a step of drying the composite material afterwashing. The drying step can be performed in the air, in an atmosphereof inert gas, in a vacuum, or the like. The drying temperature is notparticularly limited as long as it is a temperature at which the solventin the composite material can be removed to the necessary extent, and isgenerally 50 to 100° C., and preferably 60 to 90° C. The drying may beperformed by sending a wind with a dryer or the like, or may beperformed without sending a wind.

Further, in a case where a solvent having a property of swelling aporous body is used as the solvent, the porous body is restored in thedrying step. When the volume after the drying is performed after contactis taken as V2, the volume restoration rate (V2/V0) is preferably 0.3 to0.9, and more preferably 0.5 to 0.8. As described above, when the porousbody shrinks more than the original size by the drying, the compositematerial is compactly packed, and the porous coordination polymercompound that has entered the pores of the porous body hardly leaks tothe outside.

The above-described contact (permeation) step, washing step, and dryingstep may be performed only once, or may be repeated multiple times. Byperforming these steps multiple times, the porous coordination polymercompound is incorporated into the pores of the porous body each time andthe filling rate is increased. In a case where the above-described stepsare repeated multiple times, the number of repetition times is notparticularly limited, and is generally around 2 to 5 times, andpreferably around 3 or 4 times.

Internal Synthesis Method

Next, the internal synthesis method will be described. In the internalsynthesis method, at first, a porous body is prepared, and a porouscoordination polymer compound is synthesized in pores of the porousbody. The porous body can be produced by the method described in thesection of “(Method for producing porous body)”.

Next, a porous coordination polymer compound is synthesized in theprepared porous body. The synthesis of a porous coordination polymercompound can be performed in the same manner as in the section of“(Method for producing porous coordination polymer compound)”.Specifically, the synthesis can be performed by mixing and stirring ametal ion, an organic ligand, and a solvent with the porous body. Thedetails of the metal ion, the organic ligand, and the solvent are asdescribed above, the reaction temperature is also around ordinarytemperature to 300° C., the reaction time is around 30 minutes to 3weeks, and the reaction pressure is around from normal pressure to 1 to10 MPa. After the reaction, the composite material is washed and driedin a similar manner as in the above-described section of “(Washing anddrying steps)” so as to complete the composite material.

Space Filling Rate

The composite material produced in this manner can be filled in pores ofa porous body with a high space filling rate of 50% by volume or more ofa porous coordination polymer compound. The space filling rate can alsobe set to 60% by volume. The upper limit of the space filling rate isnot particularly limited, and is for example, 99% by volume or less, and95% by volume or less. In this regard, the space filling rate in thepresent specification is the result obtained by the measurement with themethod described in Examples to be described later, and specifically, isthe value obtained by measuring the mass change before and afterintroduction of the porous coordination polymer compound into the porousbody, and calculating from the ratio of the PCP volume determined fromthe mass change and the bulk density of the porous coordination polymercompound, and the void volume of the porous body.

Complex Introduction Rate: PCP Introduction Rate

Further, the composite material can be introduced with a high complexintroduction rate of 40% by mass or more, the complex introduction rate(that is, PCP introduction rate) is indicated by a mass of the porouscoordination polymer compound to the total mass of the compositematerial. The PCP introduction rate can also be set to 50% by mass. Theupper limit of the complex introduction rate is not particularlylimited, and is for example, 99% by mass or less, and 95% by mass orless. In this regard, the PCP introduction rate in the presentspecification is the result obtained by the measurement with the methoddescribed in Examples to be described later, and specifically, is thevalue obtained by measuring the mass change before and afterintroduction of the porous coordination polymer compound into the porousbody, and calculating from the ratio of the mass change and the totalmass after introduction.

As described above, the porous body of the present invention, which isobtained by copolymerizing a dialkoxysilane and a trialkoxysilane, cancarry a porous coordination polymer compound at a filling rate higherthan that of a conventional silica monolith of a tetraalkoxysilane. Thismechanism is speculated as follows.

In the conventional silica monolith of a tetraalkoxysilane, sincesilicon of a monomer has four hydrolyzable functional groups, all of thefour bonds of silicon are Si—O bonds in the polymer, the bonds aredense, and the polymer becomes hard as a carrier. For this reason,clogging is easily generated in pores when filling a porous coordinationpolymer compound that is plate-like particles having a high aspectratio, and further, it is difficult to swell the silica monolith totemporarily widen the pores and to easily introduce the porouscoordination polymer compound to the inside of the pores.

On the other hand, in the porous body of the present invention, thereare two or three functional groups (hydrolyzable functional groups) thatform Si—O bonds of an alkoxysilane monomer, and the copolymer has afunctional group (non-hydrolyzable functional group) that is notinvolved in the Si—O bond. For this reason, the porous body has a coarsebond, and therefore has a nature that is rich in flexibility.Accordingly, as described later, the pores of the porous body have astructure in which spherical particles are connected, and have smallvoids between the particles and large voids made of a connected chainstructure. Accordingly, as compared with the conventional silicamonolith of a tetraalkoxysilane, in the porous body of the presentinvention, the porous coordination polymer compound is easily filled inthe pores of the porous body, and the porous body is hardly clogged, andfurther, the porous coordination polymer compound is easily incorporatedinto the pores by swelling the porous body by using a solvent or thelike. In particular, in the present invention, two kinds of monomershaving different properties, which is a dialkoxysilane and atrialkoxysilane, are copolymerized, and therefore, the network structureof Si—O bonds is more flexible as compared with that of a homopolymerobtained by polymerizing only any one of the kinds.

In addition, the porous body of the present invention has a functionalgroup that is not involved in the Si—O bond, and therefore, byappropriately selecting the functional group, there is also an advantagethat a porous body having various characteristics can be obtained ascompared with those of the conventional silica monolith.

Volume Ratio Before and After Combination

The ratio of a volume of the composite material to a volume of theporous body before combination is preferably 1.0 or less. As describedabove, when the volume after the combination is smaller than that beforethe combination, the composite material is compactly packed, and theporous coordination polymer compound that has entered the pores of theporous body hardly leaks to the outside. The above-described volumeratio is preferably 0.3 to 0.9, and more preferably 0.5 to 0.8.

Performance of Porous Coordination Polymer Compound After Combination

With respect to the composite material according to the presentinvention, by combining a porous body obtained by copolymerizing adialkoxysilane and a trialkoxysilane, and a porous coordination polymercompound, the porous coordination polymer compound can be carried on theporous body in a state that the properties of the porous coordinationpolymer compound are maintained or improved. That is, with respect tothe composite material according to the present invention, the porouscoordination polymer compound can be carried on the porous body withoutdeteriorating the properties of the porous coordination polymer compoundas compared with the porous coordination polymer compound before thecombination.

In this regard, as the properties of the porous coordination polymercompound, for example, gas adsorption performance and the like can bementioned, and specifically, adsorption performance of carbon monoxide,and the like. In this case, the gas adsorption performance of thecomposite material after the combination has gas adsorption performancethat is equivalent to or higher than the gas adsorption performance ofthe porous coordination polymer compound alone before the combination.The gas adsorption performance can be evaluated by the amount of gasadsorption, the adsorption pressure, and the rate of pressure change. Itcan be said that as the amount of gas adsorption is larger, as theadsorption pressure is lower, and as the rate of pressure change islarger, the gas adsorption characteristic is more excellent. All ofthese gas adsorption characteristics of the composite material accordingto the present invention are equivalent to those of the porouscoordination polymer compound alone, or at least one of the gasadsorption characteristics of the composite material according to thepresent invention is superior to that of the porous coordination polymercompound alone. In addition, the gas adsorption characteristics can beevaluated by gas adsorption/desorption isotherm measurement.

3. Gas Adsorbent

The composite material according to the present invention can be usedfor various applications depending on the properties of a PCP, and inparticular, can be suitably used as a part or the whole of a gasadsorbent as described above. Examples of the gas adsorbed by the gasadsorbent include carbon monoxide gas, carbon dioxide gas, nitrogen gas,and hydrogen gas, and in particular, carbon monoxide gas is preferred.Such a carbon monoxide gas is contained as a mixed gas of hydrogen,methane, nitrogen, and carbon monoxide gas, for example, in a reformedgas such as by-product gas and petroleum natural gas at a steelworks orin petrochemicals, partial oxidation gas, a reformed gas of coal tarsand or the like, a methanol decomposition gas, or the like, and the gasadsorbent according to the present invention is suitable for applicationof selectively adsorbing only carbon monoxide gas from such a mixed gasby, for example, a pressure swing adsorption method or the like.

EXAMPLES

Hereinafter, the present invention will be described specifically by wayof Examples, however, the object of the present invention is not limitedto the following Examples. Further, in the following Examples, theexpression “%” is on a mass basis (mass percent) unless otherwiseparticularly specified.

1. Physical Property Evaluation Method (1) With Respect to Porous Body(a) Average Pore Diameter

The average pore diameter of a porous body was determined by SEMobservation. The average pore diameter was determined by assuming a porepart of the obtained SEM image to be an oval shape, and taking a lengthdistribution in the major axis direction.

(b) Void Ratio

The void ratio of a porous body was calculated by an Archimedes method.The void ratio was calculated from the ratio obtained by taking theincreased volume of a solution when the porous body was immersed inmethanol (99%) as the skeletal volume of a porous body, and taking thedifference from the volume of the porous body as the void volume.

(c) Theoretical Maximum Introduction Rate

The theoretical maximum introduction rate of a porous body wascalculated by using the following equation.

V _(pore)×ρ_(PCP) =M _(PCPMAX)

Theoretical maximum introduction rate=(M _(PCPMAX)/(M _(porous) +M_(PCPMAX)))×100   Equation

(where V_(pore): void volume of a porous body, ρ_(PCP): bulk density ofa PCP, M_(PCPMAX): theoretical maximum mass of a PCP occupying void,M_(porous): mass of a porous body, and further, at this time, ρ_(PCP)was obtained by putting 1 g of PCP in a graduated cylinder, tapping onthe PCP with a weight of 100 g to fill the graduated cylinder with thePCP, and measuring the volume.)

(2) With Respect to Composite Material (a) Space Filling Rate

The space filling rate of a composite material was obtained by measuringthe mass change before and after introduction of a PCP, and calculatingfrom the ratio of a PCP volume determined from the mass change and thebulk density of the PCP, and a void volume of a porous body.

(b) PCP Introduction Rate

The PCP introduction rate of a composite material was obtained bymeasuring the mass change before and after introduction of a PCP, andcalculating from the ratio of the mass change and the total mass afterintroduction. In this regard, depending on the measurement method ofbulk density, the degree of packing of a PCP in a porous body may exceed100% because there is also a PCP being partially immobilized on theouter surface of the porous body.

2. Example 1 (1) Synthesis of Porous Body

A porous body was synthesized according to the scheme of the followingchemical formula. Specifically, at first, 5.0 g of urea and 1.0 g ofhexadecyltrimethylammonium chloride (CTAC) were dissolved in 15 ml of a5 mM acetic acid aqueous solution, 25 mmol of vinyltrimethoxysilane(VTMS) and 10 mmol of vinylmethyldimethoxysilane (VMDMS) were added intothe above-obtained mixture, and the resultant mixture was stirred atroom temperature for 60 minutes to cause a sol reaction. Aftercompletion of the reaction, the obtained mixture was left to stand at353 K for 9 hours and aged to cause a gel reaction. The obtained gel waswashed with methanol, and the resultant gel was dried at 353 K for 1hour in the air to obtain a porous body. When physical properties of theobtained porous body were measured by the above-described physicalproperty measurement method, the average pore diameter was 13.8 μm, thevoid ratio was 84.5% by volume, and the theoretical maximum introductionrate of the following PCP-1 was 74.8% by mass.

(2) Synthesis of Porous Coordination Polymer Compound (PCP-1)

The PCP-1 was synthesized by a solution method. One mmol of coppernitrate trihydrate and 1 mmol of 5-heptafluoropropyl isophthalic acidwere dissolved in a mixed solvent of 15 ml of methanol and 5 ml of ionexchanged water, 81 μl of pyridine was added into the obtained mixturewhile stirring, and then the resultant mixture was stirred at 353K for12 hours. The solution after the reaction was filtered, the obtainedproduct was washed with methanol, and the resultant product was dried at353 K for 3 hours in the air to obtain a PCP-1. The yield was 26.6%, theaverage particle diameter was 3.7 μm, and the thickness was 0.8 μm.

(3) Preparation of Composite Material

The above-obtained PCP-1 in an amount of 120 mg was mixed with 1 mL ofmethanol to adjust a suspension. A cylindrical porous body (90 mg) wasimmersed in the obtained suspension, and was left to stand at roomtemperature for 5 minutes in this state so that the suspension permeateda gel. After that, the gel was taken out from the suspension, and theobtained gel was washed with methanol, and the resultant gel was driedat 80° C. for 1 hour in the air. These permeation, washing and dryingoperations were repeated four more times to obtain a composite materialin which the PCP-1 was carried on the porous body. When physicalproperties of the obtained composite material were measured by aphysical property measurement method, the space filling rate was 112.8%by volume, and the PCP introduction rate was 77% by mass.

(4) Electron Micrographs of Porous Body and Composite Material

By using the obtained porous body and composite material, a sample formeasurement was prepared by placing a small amount of a composite sampleon a carbon paste, and then subjecting the composite sample to platinumvapor deposition, as, SEM photographs were taken by using a scanningelectron microscope (FE-SEM SU8010 manufactured by HitachiHigh-Technologies Corporation). The results are shown in FIG. 1. Theupper part of FIG. 1 shows a photograph of the porous body beforecombination, and the lower part of FIG. 1 shows a photograph of thecomposite material after combination. As can be understood from thesephotographs, the porous body of the present invention has a structure inwhich spherical particles are connected botryoidally in a chain state,and has a structure in which large voids exist from the surface to theinside of the porous body between the chains. Further, it can beunderstood that the PCP-1 that is in a state of plate-like particles iscarried on the inner surface of the void in the porous body (that is,particulate concave-convex part), and is highly filled also in the poresin the porous body.

(5) Evaluation for Gas Adsorption Performance of Composite Material

By using the obtained composite material, the adsorption activity ofcarbon monoxide was measured. Specifically, the measurement wasperformed by CO adsorption/desorption isotherm measurement at 265 K. Theresults are shown in FIG. 3 (solid line: PCP-1 composite).

3. Comparative Example 1 (1) Synthesis of Silica Monolith

A silica monolith was obtained by a sol-gel method accompanied by phaseseparation. Specifically, at first, 46.3 ml of ion exchanged water and3.24 ml of 69% by mass nitric acid were stirred at 273 K for 15 minutes.Into the obtained mixture, while stirring, 4.79 g of polyethylene glycol(molecular weight: 35000) was added, and the resultant mixture wasstirred at 273 K for 1 hour. Further, into the obtained mixture, whilestirring, 37.7 g of tetraethoxysilane was added, and the resultantmixture was stirred at 273 K for 1 hour. The obtained mixture was leftto stand at 313 K for 3 days and aged to be turned into a gel. Theproduced gel was washed with ion exchanged water and methanol, and thenthe resultant gel was dried at 353 K for 12 hours to obtain a silicamonolith. When physical properties of the obtained silica monolith weremeasured by the above-described physical property measurement method,the average pore diameter was 5 μm, the void ratio was 43.0% by volume,and the theoretical maximum introduction rate of the following PCP-2 was36.4% by mass.

(2) Preparation of Composite Material

By using the silica monolith obtained above, a composite material wasobtained by an internal synthesis method. A solution obtained bydissolving 500 mg of copper nitrate trihydrate in 2 ml of ethanol wasadded to 90 mg of silica monolith, the obtained mixture was left tostand at 373 K for 1 hour, and then the solution was removed from theresultant mixture, and the obtained product was vacuum dried at 373 Kfor 1 hour to obtain a copper nitrate-containing silica monolith. Afterthat, into the obtained copper nitrate-containing silica monolith, asolution obtained by dissolving 150 mg of 5-heptafluoropropylisophthalic acid in 2 ml of methanol, 0.8 ml of ion exchanged water, and8 μ1 of pyridine was added, and the obtained mixture was left to standat 348 K for 12 hours to synthesize the PCP inside pores. The monolithafter the reaction was washed with methanol, and then the resultantproduct was vacuum dried at ordinary temperature for 3 hours to obtain acomposite material. When physical properties of the obtained compositematerial were measured by a physical property measurement method, thespace filling rate was 43.7% by volume, and the amount of the introducedPCP was 20.0% by mass.

(3) Evaluation for Gas Adsorption Performance of Composite Material

By using the obtained composite material, the adsorption activity ofcarbon monoxide was measured in the same manner as in Example 1. Theresults are shown in FIG. 3 (dotted line: monolith composite).

4. Reference Example 1 (1) Evaluation for Gas Adsorption Performance ofPCP-1 Alone

By using the PCP-1 obtained in Example 1, the adsorption activity ofcarbon monoxide was measured in a similar manner as in Example 1. Theresults are shown in FIG. 3 (dashed line: PCP-1).

From the results of measurement of physical properties in Example 1 andComparative Example 1, it was found that the composite material obtainedby using the porous body of Example 1 is superior both in the spacefilling rate of PCP-1 and the introduction rate of PCP, as compared withthe case of using the silica monolith of Comparative Example 1.According to this, it was found that by using a porous body as a shapingmaterial, the PCP-1 was able to be filled in high density.

In addition, from the results of the hysteresis curve of FIG. 3, whencompared the porous body (Example 1) with the silica monolith(Comparative Example 1), it was found that by using the porous body as ashaping material, the absolute value of the adsorption amount of carbonmonoxide per unit mass of the introduced PCP was larger, the pressure atthe time of adsorption and desorption was on the lower pressure side,and further the pressure change (inclination of the curve) at the timeof adsorption and desorption was sharper, as compared with those of thesilica monolith. That is, it was found that the porous body is superiorto the silica monolith in the adsorption and desorption characteristics.

Further, it was found that when compared the porous body (Example 1)with the PCP-1 alone (Reference Example 1), by combining the porous bodywith the PCP-1, carbon monoxide was adsorbed and desorbed on the lowerpressure side as compared with that of the PCP-1 alone. According tothis, it is considered that by a synergistic effect of both of theporous body and the PCP-1 due to the combination of the porous body andthe PCP-1, the carbon monoxide was able to be adsorbed and desorbed onthe lower pressure side as compared with that of the PCP-1 alone, andthe adsorption and desorption characteristics were improved.

With respect to the synergistic effect, it is considered that byimmobilizing the PCP-1 in pores of the porous body, the structuralchange of PCP during CO adsorption was adequately limited, and the gatebecame in a state suitable for CO adsorption, and therefore, excellentadsorption characteristics were exhibited. Alternatively, it isconsidered that when the PCP-1 was introduced into pores of the porousbody, the PCP having a particle size excellent for the adsorption of COwas selectively incorporated, and therefore, excellent adsorptioncharacteristics were exhibited.

5. Example 2 (1) Synthesis of Porous Coordination Polymer Compound(PCP-2)

A PCP-2 was synthesized by a solution method. Specifically, 6 g ofcopper nitrate trihydrate and 3 g of 1,3,5-benzenetricarboxylic acidwere dissolved in 100 ml of ethanol, and the obtained mixture wasstirred at 353 K for 12 hours. The precipitated precipitate wascollected by centrifugation, and the collected precipitate was washedwith ethanol three times. After that, the resultant precipitate wasdried at 353 K for 4 hours in the air to obtain a PCP-2.

(2) Preparation of Composite Material

The above-obtained PCP-2 in an amount of 120 mg was mixed with 1 ml ofmethanol to prepare a suspension. In addition, separately, the porousbody of Example 1 was cut to a piece with a cylindrical shape to preparea sample. The sample (90 mg) of the porous body was immersed in theobtained suspension, and was left to stand at room temperature for 5minutes in this state so that the suspension permeated a gel. Afterthat, the gel was taken out from the suspension, and the obtained gelwas washed with methanol, and the resultant gel was dried at 80° C. for1 hour in the air. These permeation, washing and drying operations wererepeated four more times to obtain a composite material in which thePCP-2 was carried on the porous body. When physical properties of theobtained composite material were measured by a physical propertymeasurement method, the space filling rate was 109% by volume, and thePCP introduction rate was 83.4% by mass.

(3) Evaluation of Volume Expansion Rate and Volume Restoration RateUsing Suspension

In the process of the above-described section of “(2) Preparation ofcomposite material”, the volume expansion rate of the suspensioncontaining PCP-2 and a porous body, and the volume restoration rateafter drying were measured. With respect to the cylindrical porous body,the diameter (d=2R) of a circle on the end face was 1.40 cm, the height(h) was 1.0 cm, and the initial volume (V0) calculated from the radius“R” and the height “h” was 1.54 cm³. Next, the volume of the compositematerial after immersion in the suspension was measured. The diameter(d=2R) of the circle was 1.55 cm, the height (h) was 1.1 cm, the volume(V1) after expansion was 2.08 cm³, and the volume expansion rate (V1/V0)was 1.35 times. In the end, the volume of the composite material afterdrying was measured. The diameter (d=2R) of the circle was 1.20 cm, theheight (h) was 0.8 cm, the volume (V2) after drying was 0.91 cm³, andthe volume restoration rate (V2/V0) was 0.59 times.

(4) Evaluation of Volume Expansion Rate and Volume Restoration RateUsing Organic Solvent (Reference Example 2)

By using a solvent of only 99% methanol to which the PCP-2 had not beenadded, the volume expansion rate and the volume restoration rate wereevaluated by the procedures in a similar manner as in theabove-described section of “(3) Evaluation of volume expansion rate andvolume restoration rate using suspension”. As a result, the initialvolume (V0) was 1.33 cm³, the volume (V1) after expansion afterimmersion in the solvent was 1.82 cm³, the volume expansion rate (V1/V0)was 1.37 times, the volume (V2) after drying was 1.33 cm³, and thevolume restoration rate (V2/V0) was 1.00 time.

When compared the volume expansion rate and volume restoration rate ofExample 2 with those of Reference Example 2, the volume expansion ratesin both of Example 2 and Reference Example 2 were around 1.3 times andapproximately equal to each other, and the volume restoration rate wasaround 0.6 in Example 2 and 1 time in Reference Example 2. That is, itis considered that by adding a PCP to an organic solvent, the volume wasreduced due to the interaction between the PCP and a porous body. Asdescribed above, it is considered that when a porous body was immersedin a suspension containing an organic solvent, the porous body wasswelled and the PCP easily entered the inside of the porous body, andwhen the composite material after the immersion was dried, the volumewas reduced as compared with the initial volume of the porous body dueto the interaction between the PCP and the porous body, and the PCPinside the porous body was hardly flowed to the outside.

(5) Evaluation for Gas Adsorption Performance of Composite Material

By using the composite material obtained in Example 2, the adsorptionactivity of carbon monoxide was measured in a similar manner as inExample 1. The results are shown in FIG. 4 (solid line: PCP-2composite).

(6) Evaluation for Gas Adsorption Performance of PCP-2 Alone (ReferenceExample 3)

By using the PCP-2 obtained in Example 2, the adsorption activity ofcarbon monoxide was measured in a similar manner as in Example 1. Theresults are shown in FIG. 4 (dashed line: PCP-2).

From the results of measurement of adsorption activity of Example 2 andReference Example 3, it was found that the composite material of Example2 exhibited the adsorption activity of carbon monoxide that wasequivalent to that of Reference Example 3. The results support thepresent invention in which a PCP can be carried in a state that theproperties of the PCP are maintained or improved.

6. Example 3 (1) Synthesis of Porous Body

By using dimethyldimethoxysilane (DMDMS) and 4-(trimethoxysilyl)butanenitrile, a porous body was obtained by a sol-gel method accompanied byphase separation. Specifically, 5.0 g of urea and 1.0 g ofhexadecyltrimethylammonium chloride (CTAC) were dissolved in 15 ml of a5 mM acetic acid aqueous solution, 0.21 mol of 4-(trimethoxysilyl)butanenitrile and 0.14 mol of dimethyldimethoxysilane (DMDMS) were added intothe above-obtained mixture, and the resultant mixture was stirred atroom temperature for 60 minutes to cause a sol reaction. Aftercompletion of the reaction, the obtained mixture was left to stand at353 K for 9 hours and aged to cause a gel reaction. The obtained gel waswashed with methanol, and the resultant gel was dried at 353 K for 1hour in the air to obtain a porous body. When physical properties of theobtained porous body were measured by the above-described physicalproperty measurement method, the void ratio was 71.7% by volume.

(2) Preparation of Composite Material

By using the porous body obtained above and a PCP, a composite materialwas obtained by an external synthesis method. Specifically, at first,PCP-3 (K15037 manufactured by Nippon Steel & Sumitomo Metal Corporation)was obtained. The PCP-3 is a porous coordination polymer compound havinga structure equivalent to that of PCP-1, and has an average particlediameter of 26 μm and a thickness of 5.9 μm. Next, the PCP-3 (120 mg)was mixed with 1 ml of methanol to prepare a suspension. In addition,separately, the porous body of Example 3 was cut to a piece with acylindrical shape to prepare a sample. The sample (90 mg) of the porousbody was immersed in the obtained suspension, and was left to stand atroom temperature for 5 minutes in this state so that the suspensionpermeated a gel. After that, the gel was taken out from the suspension,and the obtained gel was washed with methanol, and the resultant gel wasdried at 80° C. for 1 hour in the air. These permeation, washing anddrying operations were repeated four more times to obtain a compositematerial in which the PCP-3 was carried on the porous body. Whenphysical properties of the obtained composite material were measured bya physical property measurement method, the space filling rate was 65.3%by volume, and the PCP introduction rate was 69.2% by mass.

7. Example 4 (1) Synthesis of Porous Body

By using dimethyldimethoxysilane (DMDMS), vinyltrimethoxysilane (VTMS),and 4-(trimethoxysilyl)butane nitrile, a porous body was obtained by asol-gel method accompanied by phase separation. Specifically, 5.0 g ofurea and 1.0 g of hexadecyltrimethylammonium chloride (CTAC) weredissolved in 15 ml of a 5 mM acetic acid aqueous solution, 0.126 mol of4-(trimethoxysilyl)butane nitrile, 0.084 mol of vinyltrimethoxysilane(VTMS), and 0.14 mol of dimethyldimethoxysilane (DMDMS) were added intothe above-obtained mixture, and the resultant mixture was stirred atroom temperature for 60 minutes to cause a sol reaction. Aftercompletion of the reaction, the obtained mixture was left to stand at353 K for 9 hours and aged to cause a gel reaction. The obtained gel waswashed with methanol, and the resultant gel was dried at 353 K for 1hour in the air to obtain a porous body. When physical properties of theobtained porous body were measured by the above-described physicalproperty measurement method, the void ratio was 86.5% by volume.

(2) Preparation of Composite Material

By using the porous body obtained above and a PCP-3 of Example 3, acomposite material was obtained by an external synthesis method.Specifically, the PCP-3 (120 mg) was mixed with 1 ml of methanol toprepare a suspension. In addition, separately, the porous body ofExample 4 was cut to a piece with a cylindrical shape to prepare asample. The sample (90 mg) of the porous body was immersed in theobtained suspension, and was left to stand at room temperature for 5minutes in this state so that the suspension permeated a gel. Afterthat, the gel was taken out from the suspension, and the obtained gelwas washed with methanol, and the resultant gel was dried at 80° C. for1 hour in the air to obtain a composite material in which the PCP-3 hadbeen carried on the porous body. When physical properties of theobtained composite material were measured by a physical propertymeasurement method, the space filling rate was 85.5% by volume, and thePCP introduction rate was 80.1% by mass.

8. Example 5 (1) Synthesis of Porous Body

By using dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane, and4-(trimethoxysilyl)butane nitrile, a porous body was obtained by asol-gel method accompanied by phase separation. Specifically, 5.0 g ofurea and 1.0 g of hexadecyltrimethylammonium chloride (CTAC) weredissolved in 15 ml of a 5 mM acetic acid aqueous solution, 0.126 mol of4-(trimethoxysilyl)butane nitrile, 0.084 mol of methyltrimethoxysilane(MTMS), and 0.14 mol of dimethyldimethoxysilane (DMDMS) were added intothe above-obtained mixture, and the resultant mixture was stirred atroom temperature for 60 minutes to cause a sol reaction. Aftercompletion of the reaction, the obtained mixture was left to stand at353 K for 9 hours and aged to cause a gel reaction. The obtained gel waswashed with methanol, and the resultant gel was dried at 353 K for 1hour in the air to obtain a porous body. When physical properties of theobtained porous body were measured by the above-described physicalproperty measurement method, the void ratio was 84.5% by volume.

(2) Preparation of Composite Material

By using the porous body obtained above and a PCP-3 of Example 3, acomposite material was obtained by an immersion method. Specifically,the PCP-3 (120 mg) was mixed with 1 ml of methanol to prepare asuspension. In addition, separately, the porous body of Example 5 wascut to a piece with a cylindrical shape to prepare a sample. The sample(90 mg) of the porous body was immersed in the obtained suspension, andwas left to stand at room temperature for 5 minutes in this state sothat the suspension permeated a gel. After that, the gel was taken outfrom the suspension, and the obtained gel was washed with methanol, andthe resultant gel was dried at 80° C. for 1 hour in the air. Thesepermeation, washing and drying operations were repeated four more timesto obtain a composite material in which the PCP-3 was carried on theporous body. When physical properties of the obtained composite materialwere measured by a physical property measurement method, the spacefilling rate was 74.8% by volume, and the PCP introduction rate was75.8% by mass.

9. Evaluation of Composite Materials of Examples 3 to 5

When compared the composite materials of Examples 3 to 5 with oneanother, the composite material of Example 3 had a large pore diameterand therefore, easily discharged the PCP, but in contrast, the compositematerials of Examples 4 and 5 each had a relatively small pore diameterand therefore, favorably carried the PCP.

On a surface of the porous body of Example 3, opening parts of 700 to1000 μm were observed, and opening parts of 300 to 400 μm were observedon a surface of each of the porous bodies of Examples 4 and 5.

10. Concentration Change of PCP

The PCP-2 (200 mg) obtained in Example 2 was mixed with 3 ml of methanolto prepare a suspension. In addition, separately, the porous body ofExample 1 was cut to a piece with a cylindrical shape having a diameterof 1.4 cm and a height of 1.2 cm to prepare a sample (210 mg). Thesample of the porous body was immersed in the obtained suspension, andwas left to stand at room temperature for 5 minutes in this state sothat the suspension permeated a gel. After that, the gel was taken outfrom the suspension, and the obtained gel was washed with methanol, andthe resultant gel was dried at 80° C. for 1 hour in the air to obtain acomposite material in which 12% by mass of the PCP-2 had been carried onthe porous body. These permeation, washing and drying operations wererepeated two more times to obtain a composite material in which 32% bymass of the PCP-2 had been carried on the porous body, and furtherrepeated two more times (5 times in total) to obtain a compositematerial in which 50% by mass of the PCP-2 had been carried on theporous body.

In addition, XRD patterns were obtained by performing X-ray diffractionon each of the above-obtained three kinds of composite materials havingdifferent concentrations from one another. The results are shown in FIG.5. From FIG. 5, since peaks derived from a PCP were exhibited at thesame position (2θ=12.5) at any concentration, it was confirmed that thePCP was introduced into the porous body.

11. Load Characteristics Evaluation

By using the composite material obtained above, a weight with 97.4 g wasplaced on a cylindrical body to compress the composite material, andthen the weight was removed to restore the composite material. Thiscycle was repeated 5 times. The compressibility ratios at that time wereplotted in a graph. The results are shown in FIG. 6. Note that in FIG.6, the results of the compressibility ratios of only the porous body ofExample 1 were also shown (“Original” in FIG. 6). From the results inFIG. 6, it was found that there was almost no change in compressibilitycharacteristics even when the load was applied and repeated the cycle 5times. In addition, as the amount of the PCP introduced into a flexibleporous body is increased, the compressive elasticity is decreased, andthe composite material can be hardened. The composite material accordingto the present invention can be used of course for applicationsrequiring flexibility, and it can be utilized for various applicationsby adjusting the hardness by changing the amount of the PCP to beintroduced.

12. Example 6 (Internal Synthesis Method)

By using the porous body synthesized in Example 1, a PCP-1 wassynthesized by an internal synthesis method. Specifically, a solutionobtained by dissolving 500 mg of copper nitrate trihydrate in 2 ml ofethanol was added to 274.3 mg of a porous body, the obtained mixture wasleft to stand at 373 K for 1 hour, and then the solution was removed,and the resultant product was dried for 1 hour by using a drier toobtain a copper nitrate-containing porous body. After that, into theobtained copper nitrate-containing porous body, a solution obtained bydissolving 150 mg of 5-heptafluoropropyl isophthalic acid in 2 ml ofmethanol was added, and the resultant mixture was left to stand at 348 Kfor 6 hours to synthesize a PCP-1 inside pores. The monolith after thereaction was washed with methanol, and then the resultant product wasdried at ordinary temperature to obtain a composite material. Whenmeasured the yield of the PCP-1, the yield was 7.9%. In addition, whenphysical properties of the obtained composite material were measured bythe above-described physical property measurement method, the spacefilling rate was 41.4% by volume, and the PCP introduction rate was 60%by mass.

13. Example 7 (1) Synthesis of PCP-4 ((Co(MeIM)₂ (In This Regard, MeIMis 2-methylimidazole))

A PCP-4 was synthesized by a solution method. In 20 ml of ion exchangedwater, 0.45 g of cobalt nitrate hexahydrate and 5.5 g of2-methylimidazole were dissolved, and the obtained mixture was stirredat room temperature for 6 hours. The precipitated precipitate wascollected by centrifugation, and the collected precipitate was washedwith ethanol three times. After that, the resultant precipitate wasdried at 353 K for 12 hours in the air to obtain a PCP-4.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-4 obtained above, acomposite material was obtained by an external synthesis method. ThePCP-4 (120 mg) was mixed with 1 ml of methanol to prepare a suspension.In addition, separately, the porous body of Example 1 was cut to a piecewith a cylindrical shape to prepare a sample. The sample (90 mg) of theporous body was immersed in the obtained suspension, and was left tostand at room temperature for 5 minutes in this state so that thesuspension permeated a gel. After that, the gel was taken out from thesuspension, and the obtained gel was washed with methanol, and theresultant gel was dried at 80° C. for 1 hour in the air. Thesepermeation, washing and drying operations were repeated four more timesto obtain a composite material in which the PCP-4 was carried on theporous body. When physical properties of the obtained composite materialwere measured by a physical property measurement method, the spacefilling rate was 114.6% by volume, and the PCP introduction rate was64.6% by mass.

(3) Preparation of Composite Material (Case of Irradiation withUltrasonic Waves: Example 7-2)

By using the porous body of Example 1 and the PCP-4 obtained above, acomposite material was obtained by an external synthesis method. PCP-4(50 mg) was mixed with 2 ml of methanol, and then the obtained mixturewas irradiated with ultrasonic waves for 30 seconds to prepare asuspension. In addition, separately, the porous body of Example 1 wascut to a piece with a cylindrical shape to prepare a sample. The sample(52 mg) of the porous body was immersed in the obtained suspension, andthe suspension was allowed to permeate a gel for one minute. After that,the gel was taken out from the suspension, and the obtained gel wasdried at 353 K for 1 hour in the air. The above-described permeation anddrying operations were repeated again. Into the suspension, the PCP-4(20 mg) and 1 ml of methanol were added, the obtained mixture wasirradiated with ultrasonic waves for 30 seconds, and then theabove-described permeation operation was performed again, and theresultant product was dried at 353 K for 4 hours in the air to obtain acomposite material in which the PCP-4 had been carried on the porousbody. When physical properties of the obtained composite material weremeasured by a physical property measurement method, the space fillingrate was 60.0% by volume, the PCP introduction rate was 60.0% by mass,and the volume restoration rate was 0.759.

(4) Evaluation for Gas Adsorption Performance of Composite Material

By using the composite material obtained in Example 7-2, the adsorptionactivity of carbon dioxide was measured. Specifically, the measurementwas performed by CO₂ adsorption/desorption isotherm measurement at 298K. The results are shown in FIG. 7 (solid line: PCP-4 composite).

(5) Evaluation for Gas Adsorption Performance of PCP-4 Alone (ReferenceExample 4)

By using the PCP-4 obtained in Example 7, the adsorption activity ofcarbon dioxide was measured in a similar manner as in Example 7. Theresults are shown in FIG. 7 (dashed line: PCP-4).

From the results of measurement of adsorption activity of Example 7 andReference Example 4, it was found that the composite material of Example7 exhibited the adsorption activity of carbon dioxide that wasapproximately equivalent to that of Reference Example 4. The resultssupport the present invention in which a PCP can be carried in a statethat the properties of the PCP are maintained or improved.

14. Example 8 (1) Synthesis of PCP-5 ((Zr₆O₄(OH)₄(BDC)₆ (In This Regard,BDC is 1,4-benzenedicarboxylic acid))

A PCP-5 was synthesized by a solvothermal method. In 40 ml ofdimethylformamide, 1.60 mmol of zirconium chloride and 1.60 mmol ofterephthalic acid were dissolved, and the resultant mixture was heatedat 393 K for 24 hours in an autoclave to perform the reaction. Theprecipitated precipitate was filtered, and the obtained precipitate waswashed with dimethylformamide. After the methanol exchange, theresultant product was vacuum dried for 12 hours to obtain a PCP-5.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-5 obtained above, acomposite material was obtained by an external synthesis method. ThePCP-5 (120 mg) was mixed with 1 ml of methanol to prepare a suspension.In addition, separately, the porous body of Example 1 was cut to a piecewith a cylindrical shape to prepare a sample. The sample (90 mg) of theporous body was immersed in the obtained suspension, and was left tostand at room temperature for 5 minutes in this state so that thesuspension permeated a gel. After that, the gel was taken out from thesuspension, and the obtained gel was washed with methanol, and theresultant gel was dried at 80° C. for 1 hour in the air. Thesepermeation, washing and drying operations were repeated four more timesto obtain a composite material in which the PCP-5 was carried on theporous body. When physical properties of the obtained composite materialwere measured by a physical property measurement method, the spacefilling rate was 67.0% by volume, and the PCP introduction rate was56.1% by mass.

(3) Preparation of Composite Material (Case of Irradiation withUltrasonic Waves: Example 8-2)

By using the porous body of Example 1 and the PCP-5 obtained above, acomposite material was obtained by an external synthesis method. PCP-5(70 mg) was mixed with 2 ml of methanol, and then the obtained mixturewas irradiated with ultrasonic waves for 30 seconds to prepare asuspension. In addition, separately, the porous body of Example 1 wascut to a piece with a cylindrical shape to prepare a sample. The sample(62 mg) of the porous body was immersed in the obtained suspension, andthe suspension was allowed to permeate a gel for one minute. After that,the gel was taken out from the suspension, and the obtained gel wasdried at 353 K for 1 hour in the air. The above-described permeation anddrying operations were repeated again. Into the suspension, the PCP-5(20 mg) and 1 ml of methanol were added, the obtained mixture wasirradiated with ultrasonic waves for 30 seconds, and then theabove-described permeation operation was performed again, and theresultant product was dried at 353 K for 4 hours in the air to obtain acomposite material in which the PCP-4 had been carried on the porousbody. When physical properties of the obtained composite material weremeasured by a physical property measurement method, the space fillingrate was 48.1% by volume, the PCP introduction rate was 61.7% by mass,and the volume restoration rate was 0.570.

(4) Evaluation for Gas Adsorption Performance of Composite Material

By using the composite material obtained in Example 8-2, the adsorptionactivity of carbon dioxide was measured. Specifically, the measurementwas performed by CO₂ adsorption/desorption isotherm measurement at 298K. The results are shown in FIG. 8 (solid line: PCP-5 composite).

(5) Evaluation for Gas Adsorption Performance of PCP-5 Alone (ReferenceExample 5)

By using the PCP-5 obtained in Example 8, the adsorption activity ofcarbon dioxide was measured in a similar manner as in Example 8. Theresults are shown in FIG. 8 (dashed line: PCP-5).

From the results of measurement of adsorption activity of Example 8 andReference Example 5, it was found that the composite material of Example8 exhibited the adsorption activity of carbon dioxide that wasapproximately equivalent to that of Reference Example 5. The resultssupport the present invention in which a PCP can be carried in a statethat the properties of the PCP are maintained or improved.

15. Example 9 (1) Synthesis of PCP-6 ((Zr₆O₄(OH)₄(BDC-NH₂)₆ (In ThisRegard, BDC-NH₂ is 2-aminoterephthalic acid))

A PCP-6 was synthesized by a solvothermal method. In a mixture of 1.5 mlof hydrogen chloride and 155.2 ml of dimethylformamide, 3.50 g ofzirconium chloride and 2.72 g of 2-aminoterephthalic acid weredissolved, and the resultant mixture was heated at 393 K for 24 hours inan autoclave to perform the reaction. The precipitated precipitate wasfiltered, and the obtained precipitate was washed withdimethylformamide. After the methanol exchange, the resultant productwas vacuum dried for 12 hours to obtain a PCP-6.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-6 obtained above, acomposite material was obtained by an external synthesis method. ThePCP-6 (120 mg) was mixed with 1 ml of methanol to prepare a suspension.In addition, separately, the porous body of Example 1 was cut to a piecewith a cylindrical shape to prepare a sample. The sample (90 mg) of theporous body was immersed in the obtained suspension, and was left tostand at room temperature for 5 minutes in this state so that thesuspension permeated a gel. After that, the gel was taken out from thesuspension, and the obtained gel was washed with methanol, and theresultant gel was dried at 80° C. for 1 hour in the air. Thesepermeation, washing and drying operations were repeated four more timesto obtain a composite material in which the PCP-6 was carried on theporous body. When physical properties of the obtained composite materialwere measured by a physical property measurement method, the spacefilling rate was 105.9% by volume, and the PCP introduction rate was73.0% by mass.

16. Example 10 (1) Synthesis of PCP-7 ((Fe₃F(H₂O)₂O(BDC)₃ (In ThisRegard, BDC is 1,4-benzenedicarboxylic acid))

A PCP-7 was synthesized by a solvothermal method. In a mixture of 50 μlof 5M hydrofluoric acid and 40 ml of dimethylformamide, 1 mmol ofiron(III) chloride hexahydrate and 2 mmol of terephthalic acid weredissolved, and the resultant mixture was heated at 383 K for 24 hours inan autoclave to perform the reaction. The precipitated precipitate wasfiltered, and the obtained precipitate was washed withdimethylformamide. After the methanol exchange, the resultant productwas vacuum dried for 12 hours to obtain a PCP-7.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-7 obtained above, acomposite material was obtained by an external synthesis method. ThePCP-7 (120 mg) was mixed with 1 ml of methanol to prepare a suspension.In addition, separately, the porous body of Example 1 was cut to a piecewith a cylindrical shape to prepare a sample. The sample (90 mg) of theporous body was immersed in the obtained suspension, and was left tostand at room temperature for 5 minutes in this state so that thesuspension permeated a gel. After that, the gel was taken out from thesuspension, and the obtained gel was washed with methanol, and theresultant gel was dried at 80° C. for 1 hour in the air. Thesepermeation, washing and drying operations were repeated four more timesto obtain a composite material in which the PCP-7 was carried on theporous body. When physical properties of the obtained composite materialwere measured by a physical property measurement method, the spacefilling rate was 39.1% by volume, the PCP introduction rate was 46.4% bymass, and the volume restoration rate was 0.735.

(3) Evaluation for Gas Adsorption Performance of Composite Material

By using the composite material obtained in Example 10, the adsorptionactivity of carbon dioxide was measured. Specifically, the measurementwas performed by CO₂ adsorption/desorption isotherm measurement at 298K. The results are shown in FIG. 9 (solid line: PCP-7 composite).

(4) Evaluation for Gas Adsorption Performance of PCP-7 Alone (ReferenceExample 6)

By using the PCP-7 obtained in Example 10, the adsorption activity ofcarbon dioxide was measured in a similar manner as in Example 10. Theresults are shown in FIG. 9 (dashed line: PCP-7).

From the results of measurement of adsorption activity of Example 10 andReference Example 6, it was found that the composite material of Example10 exhibited the adsorption activity of carbon dioxide that wasequivalent to that of Reference Example 6. The results support thepresent invention in which a PCP can be carried in a state that theproperties of the PCP are maintained or improved.

17. Example 11 (1) Synthesis of Porous Body

By using vinyltrimethoxysilane (VTMS), 4-(trimethoxysilyl)butanenitrile, and vinylmethyldimethoxysilane (VMDMS), a porous body wasobtained by a sol-gel method accompanied by phase separation. In 15 mlof a 5 mM acetic acid aqueous solution, 5.0 g of urea and 1.0 g ofhexadecyltrimethylammonium chloride (CTAC) were dissolved, 0.126 mol ofvinyltrimethoxysilane (VTMS), 0.084 mol of 1,4-(trimethoxysilyl)butanenitrile, and 0.14 mol of vinylmethyldimethoxysilane (VMDMS) were addedinto the above-obtained mixture, and the resultant mixture was stirredat room temperature for 60 minutes to cause a sol reaction. Aftercompletion of the reaction, the obtained mixture was left to stand at353 K for 9 hours and aged to cause a gel reaction. The obtained gel waswashed with methanol and water, and the resultant gel was dried at 353 Kfor 1 hour in the air to obtain a porous body. The void ratio of theobtained porous body was 91.9% by volume.

(2) Preparation of Composite Material

By using the porous body obtained above and a PCP-3 of Example 3, acomposite material was obtained by an external synthesis method. ThePCP-3 (120 mg) was mixed with 1 ml of methanol to prepare a suspension.In addition, separately, the above-obtained porous body was cut to apiece with a cylindrical shape to prepare a sample. The sample (90 mg)of the porous body was immersed in the obtained suspension, and was leftto stand at room temperature for 5 minutes in this state so that thesuspension permeated a gel. After that, the gel was taken out from thesuspension, and the obtained gel was washed with methanol, and theresultant gel was dried at 80° C. for 1 hour in the air. Thesepermeation, washing and drying operations were repeated four more timesto obtain a composite material in which the PCP-3 was carried on theporous body. The space filling rate of the obtained composite was 79.8%by volume, and the PCP introduction rate was 79.4% by mass.

18. Example 12 (1) Synthesis of PCP-E (Al(OH)(BDC-NH₂) (In This Regard,BDC-NH₂ is 2-aminoterephthalic acid))

A PCP-E was synthesized by a solvothermal method. In a mixture of 29 mlof dimethylformamide and 1 ml of water, 0.76 g of aluminum(III) chloridehexahydrate and 0.56 g of 2-aminoterephthalic acid were dissolved, andthe obtained mixture was irradiated with ultrasonic waves for 15minutes, and then the resultant mixture was heated at 423 K for 24 hoursin an autoclave to perform the reaction. The precipitated precipitatewas filtered, and the obtained precipitate was washed with methanol.After that, the resultant precipitate was dried at 353 K overnight toobtain a PCP-E.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-E obtained above, acomposite material was obtained by an external synthesis method. ThePCP-E (60 mg) was mixed with 2 ml of methanol to prepare a suspension.In addition, separately, the porous body of Example 1 was cut to a piecewith a cylindrical shape to prepare a sample. The sample (53 mg) of theporous body was immersed in the obtained suspension, and the suspensionwas allowed to permeate a gel for one minute. After that, the gel wastaken out from the suspension, and the obtained gel was dried at 353 Kfor 1 hour in the air. The above-described permeation and dryingoperations were repeated again. Into the suspension, the PCP-E (20 mg)and ml of methanol were added, the above-described permeation operationwas performed again on the obtained mixture, and the resultant productwas dried at 353 K for 4 hours in the air to obtain a composite materialin which the PCP-E had been carried on the porous body. When physicalproperties of the obtained composite material were measured by aphysical property measurement method, the space filling rate was 38.0%by volume, the PCP introduction rate was 50.7% by mass, and the volumerestoration rate was 0.862.

(3) Evaluation for Gas Adsorption Performance of Composite Material

By using the composite material obtained in Example 12, the adsorptionactivity of carbon dioxide was measured. Specifically, the measurementwas performed by CO₂ adsorption/desorption isotherm measurement at 298K. The results are shown in FIG. 10 (solid line: PCP-E composite).

(4) Evaluation for Gas Adsorption Performance of PCP-E Alone (ReferenceExample 7)

By using the PCP-E obtained in Example 12, the adsorption activity ofcarbon dioxide was measured in a similar manner as in Example 12. Theresults are shown in FIG. 10 (dashed line: PCP-E).

From the results of measurement of adsorption activity of Example 12 andReference Example 7, it was found that the composite material of Example12 exhibited the adsorption activity of carbon dioxide that was slightlyhigher than that of Reference Example 7. The results support the presentinvention in which a PCP can be carried in a state that the propertiesof the PCP are maintained or improved.

19. Example 13 (1) Synthesis of PCP-F (Al₃OCl(H₂O)₂(BDC-NH₂)₃ (In ThisRegard, BDC-NH₂ is 2-aminoterephthalic acid))

A PCP-F was synthesized by a solvothermal method. In 80 ml ofdimethylformamide, 0.97 g of aluminum(III) chloride hexahydrate and 1.09g of 2-aminoterephthalic acid were dissolved, and the obtained mixturewas irradiated with ultrasonic waves for 15 minutes, and then theresultant mixture was stirred at room temperature for 1 hour. Afterthat, the mixture was heated at 393 K for 24 hours in an autoclave toperform the reaction. The precipitated precipitate was filtered, and theobtained precipitate was washed with methanol. The resultant precipitatewas dried at 353 K for 12 hours to obtain a PCP-C.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-F obtained above, acomposite material was obtained by an external synthesis method. PCP-F(70 mg) was mixed with 2 ml of methanol, and then the obtained mixturewas irradiated with ultrasonic waves for 30 seconds to prepare asuspension. In addition, separately, the porous body of Example 1 wascut to a piece with a cylindrical shape to prepare a sample. The sample(63 mg) of the porous body was immersed in the obtained suspension, andthe suspension was allowed to permeate a gel for one minute. After that,the gel was taken out from the suspension, and the obtained gel wasdried at 353 K for 1 hour in the air. The above-described permeation anddrying operations were repeated again. Into the suspension, the PCP-F(20 mg) and 1 ml of methanol were added, the obtained mixture wasirradiated with ultrasonic waves for 30 seconds, and then theabove-described permeation operation was performed again, and theresultant product was dried at 353 K for 4 hours in the air to obtain acomposite material in which the PCP-F had been carried on the porousbody. When physical properties of the obtained composite material weremeasured by a physical property measurement method, the space fillingrate was 33.8% by volume, the PCP introduction rate was 47.5% by mass,and the volume restoration rate was 0.735.

20. Example 14 (1) Synthesis of PCP-G (Fe₃O(BPDC)₃Cl.nH₂O (In ThisRegard, BPDC is 4,4′-biphenyldicarboxylic acid))

A PCP-G was synthesized by a solvothermal method. In 5 ml ofdimethylformamide, 0.270 g of iron(III) chloride hexahydrate and 0.242 gof 4,4′-biphenyldicarboxylic acid were dissolved, and the obtainedmixture was irradiated with ultrasonic waves for 15 minutes, and thenthe resultant mixture was heated at 423 K for 12 hours in an autoclaveto perform the reaction. The precipitated precipitate was filtered, andthe obtained precipitate was washed with methanol. The obtained powderwas dispersed in 40 ml of methanol, and the obtained dispersion wasstirred overnight. The powder was filtered, washed with methanol, andthe resultant powder was dried at 353 K for 12 hours to obtain a PCP-G.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-G obtained above, acomposite material was obtained by an external synthesis method. PCP-G(70 mg) was mixed with 2 ml of methanol, and then the obtained mixturewas irradiated with ultrasonic waves for 30 seconds to prepare asuspension. In addition, separately, the porous body of Example 1 wascut to a piece with a cylindrical shape to prepare a sample. The sample(62 mg) of the porous body was immersed in the obtained suspension, andthe suspension was allowed to permeate a gel for one minute. After that,the gel was taken out from the suspension, and the obtained gel wasdried at 353 K for 1 hour in the air. The above-described permeation anddrying operations were repeated again. Into the suspension, the PCP-G(20 mg) and 1 ml of methanol were added, the obtained mixture wasirradiated with ultrasonic waves for 30 seconds, and then theabove-described permeation operation was performed again, and theresultant product was dried at 353 K for 4 hours in the air to obtain acomposite material in which the PCP-G had been carried on the porousbody. When physical properties of the obtained composite material weremeasured by a physical property measurement method, the space fillingrate was 29.1% by volume, the PCP introduction rate was 53.7% by mass,and the volume restoration rate was 0.862.

(3) Evaluation for Gas Adsorption Performance of Composite Material

By using the composite material obtained in Example 14, the adsorptionactivity of carbon dioxide was measured. Specifically, the measurementwas performed by CO₂ adsorption/desorption isotherm measurement at 298K. The results are shown in FIG. 11 (solid line: PCP-G composite).

(4) Evaluation for Gas Adsorption Performance of PCP-G Alone (ReferenceExample 8)

By using the PCP-G obtained in Example 14, the adsorption activity ofcarbon dioxide was measured in a similar manner as in Example 14. Theresults are shown in FIG. 11 (dashed line: PCP-G).

From the results of measurement of adsorption activity of Example 14 andReference Example 8, it was found that the composite material of Example14 exhibited the adsorption activity of carbon dioxide that wasequivalent to that of Reference Example 8. The results support thepresent invention in which a PCP can be carried in a state that theproperties of the PCP are maintained or improved.

21. Example 15 (1) Synthesis of PCP-H (Ti₈O₈(OH)₄(BDC-NH₂)₆ (In ThisRegard, BDC-NH₂ is 2-aminoterephthalic acid))

A PCP-H was synthesized by a solvothermal method. In a mixture of 18 mlof dimethylformamide and 2 ml of methanol, 600 μl of tetrabutylorthotitanate and 0.500 g of 2-aminoterephthalic acid were dissolved,and the obtained mixture was irradiated with ultrasonic waves for 15minutes, and then the resultant mixture was heated at 423 K for 24 hoursin an autoclave to perform the reaction. The precipitated precipitatewas filtered, and the obtained precipitate was washed with methanol.After that, the resultant precipitate was dried at 353 K for 12 hours toobtain a PCP-H.

(2) Preparation of Composite Material

By using the porous body of Example 1 and the PCP-H obtained above, acomposite material was obtained by an external synthesis method. PCP-H(70 mg) was mixed with 2 ml of methanol, and then the obtained mixturewas irradiated with ultrasonic waves for 30 seconds to prepare asuspension. In addition, separately, the porous body of Example 1 wascut to a piece with a cylindrical shape to prepare a sample. The sample(60 mg) of the porous body was immersed in the obtained suspension, andthe suspension was allowed to permeate a gel for one minute. After that,the gel was taken out from the suspension, and the obtained gel wasdried at 353 K for 1 hour in the air. The above-described permeation anddrying operations were repeated again. Into the suspension, the PCP-H(20 mg) and 1 ml of methanol were added, the obtained mixture wasirradiated with ultrasonic waves for 30 seconds, and then theabove-described permeation operation was performed again, and theresultant product was dried at 353 K for 4 hours in the air to obtain acomposite material in which the PCP-H had been carried on the porousbody. When physical properties of the obtained composite material weremeasured by a physical property measurement method, the space fillingrate was 25.3% by volume, the PCP introduction rate was 50.8% by mass,and the volume restoration rate was 0.862.

22. Example 16 (1) Evaluation of Influence of Solvent for PreparingComposite Material

By using the porous body of Example 1 and the PCP-F obtained above, acomposite material was obtained by an external synthesis method. PCP-F(60 mg) was mixed with 2 ml of dimethylformamide, and then the obtainedmixture was irradiated with ultrasonic waves for 30 seconds to prepare asuspension. In addition, separately, the porous body of Example 1 wascut to a piece with a cylindrical shape to prepare a sample. The sample(61 mg) of the porous body was immersed in the obtained suspension, andthe suspension was allowed to permeate a gel for one minute. After that,the gel was taken out from the suspension, and the obtained gel wasdried at 353 K for 3 hours in the air. The above-described permeationand drying operations were repeated again. Into the suspension, thePCP-F (20 mg) and 1 ml of dimethylformamide were added, the obtainedmixture was irradiated with ultrasonic waves for 30 seconds, and thenthe above-described permeation operation was performed again, and theresultant product was dried at 353 K overnight in the air to obtain acomposite material in which the PCP-F had been carried on the porousbody. When physical properties of the obtained composite material weremeasured by a physical property measurement method, the space fillingrate was 36.4% by volume, the PCP introduction rate was 45.8% by mass,and the volume restoration rate was 0.735.

From the results of physical properties evaluation of compositematerials of Example 13 and Comparative Example 16, it was found that acomposite material having a high filling amount and a shrunken volumecan be obtained even when the PCP suspending solvent is changed.

The PCP (kind of metal ion+organic ligand), the porous body (kind ofmonomer), the void ratio of the porous body, the synthesis method ofPCP, the space filling rate of the composite material, and the PCPintroduction rate, which are used in the above-described Examples andComparative Example, are summarized in the following Table.

TABLE 1 PCP Volume Space intro- restor- Void Synthesis filling ductionation PCP Porous body ratio method rate rate rate Exam- PCP-1vinyltrimeth- 84.5% External 112.8% 77.0% 0.735 ple 1 (copperoxysilane + by by by nitrate vinylmethyl- volume volume masstrihydrate + dimethoxy- 5- silane heptafluoro- propyl- isophthalic acid)Exam- PCP-2 vinyltrimeth- 84.5% External   109% 83.4% 0.59 ple 2 (copperoxysilane + by by by nitrate vinylmethyl- volume volume masstrihydrate + dimethoxy- ,3,5- silane benzenetri- carboxylic acid) Exam-PCP-3 dimethyldi- 71.7% External  65.3% 69.2% — ple 3 (coppermethoxysilane + by by by nitrate 4- volume volume mass trihydrate +(trimethoxy- 5- silyl)butane heptafluoro- nitrile propyl isophthalicacid) Exam- PCP-3 dimethyldi- 86.5% External  85.5% 80.1% — ple 4(copper methoxysilane + by by by nitrate vinyltrimeth- volume volumemass trihydrate + oxysilane + 5- 4- heptafluoro- (trimethoxy- propylsilyl)butane isophthalic nitrile acid) Exam- PCP-3 dimethyldi- 84.5%External  74.8% 75.8% — ple 5 (copper methoxysilane + by by by nitratemethyltri- volume volume mass trihydrate + methoxysilane + 5- 4-heptafluoro- (trimethoxy- propyl silyl)butane isophthalic nitrile acid)Exam- PCP-1 vinyltrimeth- 84.5% Internal  41.4% 60.0% — ple 6 (copperoxysilane + by by by nitrate vinylmethyl- volume volume masstrihydrate + dimethoxy- 5- silane heptafluoro- propyl isophthalic acid)Exam- PCP-4 vinyltrimeth- 84.5% External 114.6% 64.6% ple 7 (cobaltoxysilane + by by by nitrate vinylmethyl- volume volume masshexahydrate + dimethoxy- 2- silane methylimid- azole) Exam- PCP-4vinyltrimeth- 84.5% External  60.0% 60.0% 0.759 ple 7- (cobaltoxysilane + by by by 2 nitrate vinylmethyl- volume volume masshexahydrate + dimethoxy- 2- silane methylimid- azole) Exam- PCP-5vinyltrimeth- 84.5% External  67.0% 56.1% — ple 8 (zirconium oxysilane +by by by chloride + vinylmethyl- volume volume mass terephthalicdimethoxy- acid) silane Exam- PCP-5 vinyltrimeth- 84.5% External  48.1%61.7% 0.570 ple 8- (zirconium oxysilane + by by by 2 chloride +vinylmethyl- volume volume mass terephthalic dimethoxy- acid) silaneExam- PCP-6 vinyltrimeth- 84.5% External 105.9% 73.0% — ple 9 (zirconiumoxysilane + by by by chloride + vinylmethyl- volume volume mass 2-dimethoxy- aminotereph- thallo acid) silane Exam- PCP-7 vinyltrimeth-84.5% External  39.1% 46.4% 0.735 ple 10 (iron (III) oxysilane + by byby chloride vinylmethyl- volume volume mass hexahydrate + dimethoxy-terephthalic silane acid) Exam- PCP-3 vinyltrimeth- 91.9% External 79.8% 79.4% — ple 11 (copper oxysilane + by by by nitrate 4- volumevolume mass trihydrate + (trimethoxy- 5- silyl)butane heptafluoro-nitrile + propyl vinylmethyl- isophthalic dimethoxy- acid) silane Exam-PCP-E vinyltrimeth- 84.5% External 38.01 

 

 % 50.7 

 % 0.862 ple 12 (aluminum (III) oxysilane + by chloride vinylmethyl-volume hexahydrate + dimethoxy- 2- silane aminotereph- thallo acid)Exam- PCP-F vinyltrimeth- 84.5% External  33.8% 47.5% 0.735 ple 13(aluminum (III) oxysilane + by by by chloride vinylmethyl- volume volumemass hexahydrate + dimethoxy- 2- silane aminotereph- thallo acid) Exam-PCP-G vinyltrimeth- 84.5% External  29.1% 53.7% 0.862 ple 14 (iron(III)oxysilane + by by by chloride vinylmethyl- volume volume masshexahydrate + dimethoxy- 4,4f- silane biphenyl dicarboxylic acid) Exam-PCP-H vinyltrimeth- 84.5% External  25.2% 50.8% 0.862 ple 15 (tetrabutyloxysilane + by by by orthotitanate + vinylmethyl- volume volume mass 2-dimethoxy- aminotereph- silane thallo acid) Exam- PCP-F vinyltrimeth-84.5% External  36.4% 45.8% 0.735 ple 16 (aluminum(III) oxysilane + byby by chloride vinylmethyl- volume volume mass hexahydrate + dimethoxy-2- silane aminotereph thallo acid) Com- PCP-1 tetraethoxy- 43.0%Internal  43.7% 20.0% 1.00 para- (copper silane by by by tive nitratevolume volume mass Exam- trihydrate + ple 1 5- heptafluoro- propylisophthalic acid)

As compared with Comparative Example 1 including tetraethoxysilane, withrespect to the porous body, which is obtained by copolymerizing adialkoxysilane and a trialkoxysilane, of each of Examples 1 to 16 of thepresent invention, the void ratio of the porous body is favorable, thevoid ratio is increased by as much as 28.7% by volume at least inExample 3, and in Example 11, the void ratio is increased by as much as48.9% by volume comparing to that of Comparative Example 1 and theporous body has voids twice or more those of Comparative Example 1. Asis apparent from Examples 1 to 16, regardless of the kind of the PCP,the porous body of the present invention can carry the PCP.

Further, when comparing Example 1 in which the synthesized PCP wascarried on a porous body with Example 6 in which the PCP was synthesizedin a porous body, it can be understood that carrying the synthesized PCPin a porous body is more excellent rather than synthesizing the PCP in aporous body because the space filling rate and the PCP introduction ratebecome higher.

In addition, the amount of the PCP to be carried on the porous body ofthe present invention, that is, the PCP introduction rate is increasedby 26.4% by mass even in Example 10 having the least amount comparing tothat of Comparative Example 1, and the PCP can be carried in the porousbody in an amount twice or more that of Comparative Example 1. InExample 2, the amount of the PCP to be carried is increased by 63.4% bymass, and the PCP can be carried in the porous body in an amount 4 timesor more that of Comparative Example 1.

1. A method for producing a composite material containing a porous bodyhaving pores inside the porous body and a porous coordination polymercompound, comprising carrying a porous coordination polymer compoundinto the pores of a porous body via a solvent.
 2. The method forproducing a composite material according to claim 1, further comprising:forming a dispersion liquid of a porous coordination polymer compound bydispersing the porous coordination polymer compound in the solvent; andbringing the dispersion liquid into contact with the porous body tointroduce the porous coordination polymer compound into the pores. 3.The method for producing a composite material according to claim 1,further comprising: washing the porous body to remove the porouscoordination polymer compound that has not been carried on the porousbody after the porous coordination polymer compound is brought intocontact with the porous body; and drying the porous body to remove thesolvent.
 4. The method for producing a composite material according toclaim 1, wherein the solvent has a property of swelling the porous body.5. The method for producing a composite material according to claim 4,wherein the solvent is at least one solvent selected from the groupconsisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,2-butanol, benzene, hexane, acetaldehyde, acetone, cyclohexane, andN,N-dimethylformamide.
 6. The method for producing a composite materialaccording to claim 2, wherein the porous body is brought into contactwith the dispersion liquid while being swelled.
 7. The method forproducing a composite material according to claim 2, wherein, aftercontacting the porous body with the dispersion liquid, the porous bodyis dried to remove the solvent.
 8. The method for producing a compositematerial according to claim 2, wherein when the porous body is contactedwith the dispersion liquid and a volume of the porous body before thecontact is taken as V0 and a volume of the porous body after the contactis taken as V1, a volume expansion rate, V1/V0, of the porous body is1.2 to 2.0.